The Chemical Transformations of C1 Compounds E-Book

• Herausgeber: Wiley-VCH GmbH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 2713

Veröffentlichungsjahr: 2022

Beschreibung

The Chemical Transformations of C1 Compounds

A comprehensive exploration of one-carbon molecule transformations

The chemistry of one-carbon molecules has recently gained significant prominence as the world transitions away from a petroleum-based economy to a more sustainable one. In The Chemical Transformations of C1 Compounds, an accomplished team of chemists delivers an in-depth overview of recent developments in the field of single-carbon chemistry. The three-volume book covers all major C1 sources, including carbon monoxide, carbon dioxide, methane, methanol, formic acid, formaldehyde, carbenes, C1 halides, and organometallics.

The editors have included resources discussing the main reactions and transformations into feedstock chemicals of each of the major C1 compounds reviewed in dedicated chapters. Readers will discover cutting-edge material on organic transformations with MeNO2, DMF, DCM, methyl organometallic reagents, CCl4, CHCl3, and CHBr3, as well as recent achievements in cyanation reactions via cross-coupling.

The book also offers:

• Thorough introductions to chemical transformations of CH4, methods of CH4 activation, chemical transformations of CH3OH and synthesis alkenes from CH3OH
• Comprehensive explorations of the carbonylation of MeOH, CH2O in organic synthesis, organic transformations of HCO2H, and hydrogen generation from HCO2H
• Practical discussions of the carbonylation of unsaturated bonds with heterogeneous and homogeneous catalysts, as well as the carbonylation of C(sp2)-X bonds and C(sp3)-X bonds
• In-depth examinations of carbonylative C-H bond activation and radical carbonylation

Perfect for organic and catalytic chemists, The Chemical Transformations of C1 Compounds is also an ideal resource for industrial chemists, chemical engineers, and practitioners at energy supply companies.

Leseprobe

Table of Contents

Cover

Volume I

Title Page

Copyright

1 Direct Conversions of Methane via Homogeneous Processes

1.1 Introduction

1.2 Formation of Methanol and Its Derivatives

1.3 Formation of Acetic Acid

1.4 Formation of Methanesulfonic Acid

1.5 Formation of Borylated Products

1.6 Formation of Aminated Products

1.7 Formation of Alkylated Products

1.8 Summary and Conclusions

References

2 Chemical Transformations of Methanol

2.1 Introduction

2.2 Methylation

2.3 N-Methylation

2.4 Hydroxymethylation

2.5 N-Formylation

2.6 Methoxylation

2.7 The Reactions Using Methanol as the C1 Source

2.8 Conclusions

References

3 Synthesis of Olefins from CH

3

OH

3.1 Introduction

3.2 Catalysts of Methanol to Olefins

3.3 Catalytic Reaction Mechanism of Methanol Conversion

3.4 Deactivation of MTO Reaction

3.5 DMTO Process Developments

3.6 Conclusions and Outlook

Acknowledgments

References

4 Carbonylation of Methanol: A Versatile Reaction

4.1 Introduction

4.2 Carbonylation of Methanol to Produce Acetic Acid

4.3 Conclusion and Future Aspects

Acknowledgments

References

5 Formaldehyde as C1 Synthon in Organic Synthesis

5.1 Introduction

5.2 Formaldehyde as Methylenes (–CH

2

–)

5.3 Hydroxymethylation Reagent (–CH

2

OH)

5.4 As CO Source

5.5 As Hydrogen Donor and Accepter

5.6 As Methylation and Formylation Reagents

5.7 Formaldehyde as Ligand and Reductant in Organometallic Chemistry

5.8 Summary and Outlook

References

6 Organic Transformations of HCO

2

H

6.1 Introduction

6.2 Providing Carbonyl Moiety

6.3 Providing Carboxyl Moiety

6.4 As Hydrogen Source

6.5 Other Reactions

6.6 Conclusion

References

7 The Multifunctional Materials for Heterogenous Carboxylation: From Fundamental Understanding to Industrial Applications

7.1 Introduction

7.2 Hydroformylation of Olefins

7.3 Heterogeneous Carbonylation

7.4 Other Catalytic Reactions

7.5 Summary and Perspective

Acknowledgments

Conflict of Interest

References

8 Recent Hydrocarbonylation of Unsaturated Hydrocarbons with Homogeneous Catalyst

8.1 Introduction

8.2 Transition Metal-Catalyzed Hydroformylation

8.3 Transition Metal-Catalyzed Hydrocarbonylation (Reppe Carbonylation)

Acknowledgments

List of Abbreviations

References

9 Carbonylation of C(sp

2

)—X Bonds

9.1 Introduction

9.2 Common Aspects

9.3 Domino Carbonylations

9.4 Double Carbonylations

9.5 Asymmetric Carbonylations

9.6 Applications

References

10 Carbonylation of C(sp

3

)—X Bonds Utilizing CO

10.1 Introduction

10.2 Carbonylation of Allyl Compounds

10.3 Carbonylation of Benzylic Compounds

10.4 α-Carbonylation of Carbonyl Derivatives

10.5 Carbonylation of Aliphatic Alkyl Compounds

10.6 Conclusion

References

Volume II

Title Page

Copyright

11 Carbonylative C—H Bond Activation

11.1 Introduction

11.2 Acid-Mediated Carbonylative C–H Functionalization

11.3 Transition Metal Catalyzed Carbonylative C–H Functionalization

References

12 Recent Advances in Radical Carbonylation

12.1 Tutorial Introduction

12.2 Alkyl Radical Carbonylation

12.3 Alkenyl Radical Carbonylation

12.4 Aryl Radical Carbonylation

12.5 Catalytic Alkyl Radical Carbonylation

References

13 Asymmetric Carbonylation Reactions

13.1 Introduction

13.2 Ligands for Rhodium-Catalyzed AHF of Activated Terminal Alkenes (Vinyl Acetate, Styrene, and Allyl Cyanide)

13.3 Ligands for Rhodium-Catalyzed AHF of Challenge Substrates (Unfunctionalized Terminal Alkenes, 1,1- and 1,2-Disubstituted Alkenes)

13.4 Potential Applications in Pharmaceuticals and Synthetic Organic Chemistry

13.5 Mechanistic Advances in Rhodium-Catalyzed AHF

References

14 Carbonylative Synthesis of DPC (Diphenyl Carbonate)

14.1 Introduction

14.2 Oxidative Carbonylation of Phenol to DPC Under Homogeneous Catalysis

14.3 Oxidative Carbonylation of Phenol to DPC with Heterogeneous and Supported Catalysts

14.4 Oxidative Carbonylation of Phenol to DPC with Carbon Monoxide Surrogates

14.5 Summary and Conclusions

References

15 Oxidative Carbonylation of Amines

15.1 Introduction

15.2 Mono-oxidative Carbonylation of Amines

15.3 Double Oxidative Carbonylation of Amines

15.4 Intramolecular Oxidative Carbonylation of Amines

15.5 Electrochemical Oxidative Carbonylation of Amines

15.6 Conclusion and Perspectives

References

16 Carbonylation of Nitroarenes and Related Compounds

16.1 Introduction

16.2 General Reactivity Trends

16.3 Synthesis of Base Chemicals

16.4 Synthesis of Fine Chemicals

16.5 Use of CO Surrogates

16.6 Conclusions

References

17 Zeolite-Catalyzed Carbonylation of Dimethyl Ether

17.1 Syngas to Ethanol

17.2 Methanol/DME Carbonylation

17.3 DME Carbonylation over Zeolites

17.4 Reaction Mechanism

17.5 Deactivation of HMOR

17.6 Pore Engineering

17.7 Perspectives

References

18 Complex Natural Product Total Syntheses Facilitated by Palladium-Catalyzed Carbonylative Cyclizations

18.1 Introduction

18.2 Jatrophone

18.3 3-Isorauniticine

18.4 Hirsutene

18.5 Cephanolide C

18.6 Crinipellin A

18.7 Leucascandrolide A

18.8 Callipeltoside C

18.9 Schindilactone A

18.10 Pallambins

18.11 Perseanol

18.12 Bisdehydrostemoninine

18.13 Callyspongiolide

18.14 Spinosyn A

18.15 Rhazinilam

18.16 Summary

References

19 Metal-Catalyzed Alternating Polymerization Reactions with Carbon Monoxide

19.1 Introduction

19.2 Olefin/CO Copolymerization

19.3 Alkyne/CO Copolymerization

19.4 Imine and Aziridine/CO Copolymerization

19.5 Epoxide/CO Copolymerization

19.6 Future Prospects

References

20 CO Hydrogenation

20.1 Introduction

20.2 Methanol Synthesis

20.3 Fischer–Tropsch Synthesis

20.4 Bifunctional Catalysis

20.5 Higher Alcohol Synthesis

20.6 Conclusions and Perspectives

Acknowledgments

Conflict of Interest

References

21 Carboxylation with Carbon Dioxide as a C1 Source via Carbon–Carbon Bond Forming Reactions

21.1 Introduction

21.2 Carboxylation of Unsaturated Hydrocarbons

21.3 Carboxylation of Organometallic Reagents

21.4 Carboxylation of C—X Bonds

21.5 Carboxylation of C–H Bonds

21.6 Photochemical Carboxylation Using Transition-Metal Catalysts

21.7 Conclusions and Outlook

References

22 Cyclization Reactions with CO

2

22.1 Introduction

22.2 Design and Application of Highly Active Catalyst Systems

22.3 Halide-Free Catalyst Systems

22.4 Organocatalytic Strategies

22.5 New Conceptual Routes

22.6 Photochemical Synthesis of Cyclic Carbonates

22.7 Concluding Remarks and Outlook

Acknowledgements

References

23 Reduction of CO

2

to Formic Acid

23.1 Introduction

23.2 Thermocatalytic Reduction of CO2

23.3 Electrochemical Reduction of CO2

23.4 Photocatalytic Reduction of CO2

23.5 Conclusion

References

24 Reduction of CO

2

to CO and Their Applications

24.1 Introduction to Reduction of CO

2

to CO

24.2 Direct CO

2

to CO Reduction Techniques and Applications to Synthesis

24.3 Synthesis of CO Surrogates from CO

2

and Applications in Synthesis

24.4 Conclusion and Outlook

References

Volume III

Title Page

Copyright

25 Hydrogenation of CO

2

to Chemicals with Green Hydrogen

25.1 Introduction

25.2 CO

2

Molecule and H

2

Sources

25.3 CO

2

Hydrogenation to Methanol

25.4 CO

2

Hydrogenation to Lower Olefins

25.5 CO

2

Hydrogenation to Aromatics

25.6 Summary and Future Outlook

Acknowledgments

References

26 Methylation Reactions with CO

2

26.1 Introduction

26.2

N

-Methylation

26.3

C

-Methylation

26.4

S

-Methylation

26.5 Summary and Outlook

Acknowledgments

References

27 Using CO

2

as –CH– and –CH

2

– Sources

27.1 Introduction

27.2 Using CO

2

as –CH– Sources

27.3 Using CO

2

as –CH

2

– Sources

27.4 Conclusion and Outlooks

References

28 Catalytic Asymmetric Transformation of CO

2

28.1 Introduction

28.2 Reaction with Epoxides

28.3 Reaction with Olefins

28.4 Reaction with Alkynes

28.5 Reaction with Allenes

28.6 Functionalization of C—H Bonds

28.7 Electrocatalytic Asymmetric Transformation of CO

2

28.8 Outlook

References

29 Polymerization Reactions with CO

2

29.1 Introduction

29.2 Copolymerization of CO

2

and Epoxides to Produce Polycarbonates

29.3 Copolymerization of CO

2

and Oxetane

29.4 Copolymerization of CO

2

and Aziridines

29.5 Copolymerization of CO

2

and Diamines

29.6 Multicomponent Polymerization with CO

2

29.7 Polymerization of CO

2

-Sourced Building Blocks

29.8 Summary and Concluding Remarks

References

30 Transition-Metal-Catalyzed C–CN Cross-Coupling

30.1 Introduction

30.2 Palladium-Catalyzed Cross-Coupling Reactions

30.3 Copper-Catalyzed Cross-Coupling Reactions

30.4 Nickel-Catalyzed Cross-Coupling Reactions

30.5 Rhodium-Catalyzed Cross-Coupling Reactions

30.6 Summary

References

31 Recent Advancement in Transition-Metal-Catalyzed Hydrocyanation of Nonpolar Unsaturated Compounds

31.1 Introduction

31.2 Hydrocyanation of Nonpolar Alkenes

31.3 Hydrocyanation of Nonpolar Alkynes

31.4 Hydrocyanation of Nonpolar Allenes and Dienes

31.5 Hydrocyanation of Other Unsaturated Compound, Dihydrocyanation, and Cascade Hydrocyanation

31.6 Conclusion and Perspective

References

32 Organic Transformations with MeNO

2

32.1 Introduction

32.2 Henry Reaction (Nitroaldol)

32.3 aza-Henry (nitro-Mannich) Reactions

32.4 Michael Reaction with Nitromethane

32.5 Summary and Conclusions

References

33 Applications of DMF as a Reagent in Organic Synthesis

33.1 Introduction

33.2 Source of Oxygen and Hydrogen Units

33.3 Source of Carbon Units

33.4 Source of CN Unit

33.5 Source of Carbonyl Units

33.6 Source of NMe

2

Unit

33.7 Source of C-NMe

2

Unit

33.8 Source of CHNMe

2

Unit

33.9 Source of O=C–NMe

2

Unit

33.10 Source of OHC-NMeCH

2

Unit

33.11 Conclusion

References

34 Advances in the Synthesis of Methylated Products Through Direct Approaches: A Guide for Selecting Methylation Reagents

34.1 Introduction

34.2 Methylation by Using Conventional Reagents

34.3 Monomethylation

34.4 Common Strategies for Selective N-methylation of Amino Acids and Peptides

34.5 Summary and Perspective

Conflict of Interest

Abbreviations of Methylation Reagents

References

35 Organic Transformations with DCM, CCl

4

, CHCl

3

, and CHBr

3

and Other Related Reactions

35.1 Introduction

35.2 Transformation with DCM as C1 Building Block

35.3 Transformation with CCl

4

/CBr

4

as C1 Building Block

35.4 Transformation with CHCl

3

as C1 Building Block

35.5 Transformation with CHBr

3

as C1 Building Block

References

36 Trifluoromethylation with CF

3

I and Other Related Reagents

36.1 Introduction

36.2 Trifluoromethylation with CF

3

I

36.3 Trifluoromethylation with CF

3

Br

36.4 Trifluoromethylation with CF

3

SO

2

Na

36.5 Trifluoromethylation with CF

3

SO

2

Cl

36.6 Trifluoromethylation with CF

3

H

References

37 The Applications of Dimethyl Sulfoxide as a One-Carbon Source in Organic Synthesis

37.1 Introduction

37.2 As –CH

3

Source

37.3 As –CH

2

– Source

37.4 As –C=CH

2

Source

37.5 As “=CH–” Source

37.6 As –CHO Source

37.7 As –CN Source

37.8 Summary

References

Index

End User License Agreement

List of Tables

Chapter 1

Table 1.1 Modifications on Pt catalysts for homogeneous oxidation of methane...

Table 1.2 Homogeneous oxidation of methane to methyl bisulfate under strong ...

Table 1.3 Homogeneous oxidation of methane to methyl trifluoroacetate by Pd(...

Table 1.4 Direct conversion of methane to acetic acid utilizing K

2

S

2

O

8

as th...

Table 1.5 Direct transformation of methane to acetic acid using O

2

as the ox...

Table 1.6 Direct sulfonation of methane to MSA by various initiators initiat...

Chapter 3

Table 3.1 The series of carbenium ions observed in zeolites with solid-state...

Chapter 4

Table 4.1 Results of carbonylation reaction of methanol.

Table 4.2 Results of carbonylation reaction of methanol.

Table 4.3 Results of [Rh(CO)

2

Cl(L)] catalyzed carbonylation reactions of met...

Table 4.4 Results of carbonylation reaction of methanol catalyzed by [Rh(CO)

Chapter 7

Table 7.1 The Rh/CPOL-bp&P catalyst performance in hydroformylation of buten...

Chapter 8

Table 8.1 Overview of published reviews, books, and chapters on the hydrocar...

Chapter 9

Table 9.1 Palladium-catalyzed carbobutoxylation of Ph–I, Ph–Br.

Table 9.2 The effects of ring size on the competition between C–Pd and Ac–Pd...

Chapter 10

Table 10.1 Carbonylation of allyl chlorides to esters.

Table 10.2 Alkoxycarbonylation of allyl phosphates.

Table 10.3 Carbonylation of benzyl halides to esters.

Chapter 15

Table 15.1 Platinum group metal-halide-catalyzed carbamate synthesis.

Table 15.2 Pd–phen–Im–NaY-catalyzed oxidative carbonylation of aniline.

Table 15.3 Oxidative carbonylation of amines catalyzed by Au(I) complex.

Table 15.4 The ligands effect in oxidative carbonylation.

Chapter 17

Table 17.1 Heterogeneous catalysts for methanol/DME carbonylation.

Table 17.2 DME carbonylation over zeolites.

Table 17.3 DME carbonylation over transition-metal-modified HMORs.

Table 17.4 Calculated activation energies (kJ/mol) at the DFT and DFT-D (dis...

Chapter 20

Table 20.1 Typical Cu/ZnO-based catalysts and process conditions employed in...

Chapter 23

Table 23.1 Representative performance of noble metal catalysts for hydrogena...

Table 23.2 Representative performance of non-noble metal catalysts for the h...

Table 23.3 Representative performance of heterogeneous catalysts for hydroge...

Chapter 25

Table 25.1 Some representative catalysts for the direct hydrogenation of CO

2

Table 25.2 Some typical catalysts for hydrogenation of CO

2

to lower olefins....

Table 25.3 Some representative catalysts for CO

2

hydrogenation to aromatics....

Chapter 34

Table 34.1 Synthesis of methylated products from aryl chlorides or acyl chlo...

Table 34.2 Calculated p

K

a

-guided methylation using DMF-DMA at a specific tem...

Table 34.3 Rh-catalyzed methylation of ketones.

Table 34.4 Synthesis of α-branched methylated ketones.

Table 34.5 One-pot methylation of amines/amino acids under catalytic hydroge...

Table 34.6 Photocatalytic N-methylation of amines.

Table 34.7 Photoinduced methylation of heteroarenes with MeOH in DCM/TFA.

Table 34.8 β-C(sp

3

)-Methylation of primary alcohols.

Table 34.9 Selected samples of iron-catalyzed isomerization−methylation of a...

Table 34.10 Minisci-type methylation.

Table 34.11 Direct methylation of 2-pyridones with Ac

2

O.

Table 34.12 Methyl radicals from DMSO with Fenton reagent.

Table 34.13 Formic acid as the methylation reagent.

Table 34.14 Methylation of amines with formaldehyde.

Table 34.15 C-3 methylation of quinoxalin-2(1

H

)-ones.

Table 34.16 Methylation of nitroarenes, benzoic acid derivatives, and other ...

Table 34.17 Late-stage C–H methylation with TMB.

Table 34.18 Methylation of 8-methylquinolines with MeBF

3

K.

Table 34.19 Application of lithium methyltriolborate for methylation.

Table 34.20 BpinCH

2

Bpin for N-methylated pyridines.

Table 34.21 Reductive methylation of amines with DMC.

Table 34.22 Methylation of Ar-I and Ar-Br with in situ-formed MeZnI.

Table 34.23 A Ni

II

-catalyzed methylation of amides bearing an 8-aminoquinoli...

Table 34.24 C-Methylation of carbonyl chlorides and alkyl bromides with MeOT...

Table 34.25 C-Methylation of aryl bromides with MeOTs.

Table 34.26 ortho-C-methylation of aryl amides with MeOTs.

Table 34.27 Synthesis of

N

-arylsulfonyl-

N

-methyl (

S

)-analine methyl esters.

a)

Table 34.28 Selected methylated samples using three methyl sources.

Table 34.29 Late-stage methylation of aryl-/heteroaryl inert C−H bonds.

Table 34.30 Fast cross-coupling of arylbromides with MeLi.

Table 34.31 Iron-catalyzed

ortho

-methylation of NH-Q-featured amides.

Table 34.32 Iron-catalyzed

ortho

-methylation of picolinoylamide-featured amid...

Table 34.33 Cobalt-catalyzed

ortho

-methylation using Me

3

Al.

Table 34.34 Iron-catalyzed

ortho

-methylation.

Table 34.35 Decarboxylative methylation/ethylation of

N

-(acyloxy)phthalimides...

Table 34.36 Ni-catalyzed methylation of arenols with MeMgBr.

Table 34.37 Cross-coupling reaction of benzylic esters with Me

2

Zn.

Table 34.38 Cross-coupling reaction of lactones with Me

2

Zn.

Table 34.39 Transformation of sulfonyl chlorides into thioethers.

Table 34.40 Methylation of C–H-aminated intermediates.

Table 34.41 Methylation of NH, OH, and SH with MTFA.

Table 34.42 Methyltion with TMAF.

Table 34.43 Methylation and acetylation with PEG-400.

Table 34.44 Pd-catalyzed methylation of alkynes with PhNMe

3

OTf.

Table 34.45 Mono N-methylation with DMC.

Table 34.46 Mono N-methylation in flow chemistry.

Table 34.47 Mono N-methylation of anilines via Chan–Lam cross-coupling.

Table 34.48 Chan–Lam coupling of amines/amides/thiols and RB(OH)

2

.

Table 34.49

N

-methylated products from nitrosoarenes.

Table 34.50 Mono N-methylation using the [Cp*IrCl

2

]

2

catalyst.

Table 34.51 Mono N-methylation using the ligand-installed Ir catalyst

450

.

Table 34.52 Mono N-methylation using the Ir NCs catalyst.

Table 34.53 Mono N-methylation catalyzed by NHC-Ir polymer.

Table 34.54 Mono N-methylation of nitroarenes.

Table 34.55 Mono N-methylation of anilines.

Table 34.56 Mono N-methylation through borrowing hydrogen strategy (Ru-catal...

Table 34.57 Mono N-methylation of amines using the Ru-catalyst

463

.

Table 34.58 N-Monomethylation from bromides.

Table 34.59 N-Methylated amides from primary amides.

Table 34.60 N-Methylated amides from aldoximes.

Table 34.61 N-Methylated products from acyl azides.

Table 34.62 Selected N-methylated products using catalysts

504

–

506

.

Table 34.63 N-Methylation from nitroarenes.

Table 34.64 Selective mono N-methylation of anilines using the [Re]-catalyst

Table 34.65

N

-Methylation from nitroarenes.

Table 34.66 N-Methylation from nitroarenes.

Table 34.67 N-Methylation of amines using Co(acac)

2

as the catalyst.

Table 34.68 N-Methylation from nitroarenes.

Table 34.69 Mono N-methylation of anilines with MeOH catalyzed by Pd/C.

Table 34.70 N-Methylation of nitroarenes and amines through Pd/C catalysis.

Table 34.71 In(OTf)

3

-catalyzed mono N-methylation of amines with dimthyl pho...

Table 34.72 Mono N-methylation of primary amides using trimethyl phosphate.

Table 34.73 CuI-catalyzed mono N-methylation of primary amides.

Table 34.74 Mono N-methylation of amines and amino acids.

Table 34.75 Mono N-methylation of aliphatic primary amines.

Table 34.76 N-Alkylation of amines with aldehydes.

Table 34.77 N-Alkylated products from nitroarenes.

Table 34.78 N-Methylated products through reduction of amidines.

Table 34.79 N-Methylated products through reduction of formimidate.

Table 34.80 N-Methylation of anilines by Me

3

N-BH

3

/DMF.

Table 34.81 Mono N-methylation of anilines with HOAc.

Table 34.82 N-Methylated products from nitroalkanes.

Table 34.83 N-Methylation through the reduction of carbonylimidazolides.

Table 34.84 Reduction of carbamates through Mg-catalyzed hydroboration.

Table 34.85 N-Methylation by MeOTf in HFIP.

List of Illustrations

Chapter 1

Figure 1.1 Direct conversions of methane via homogeneous processes.

Figure 1.2 Catalytic oxidation of methane in Shilov reaction.

Figure 1.3 Modification of the Shilov reaction with (bpym)PtCl

2

complex.

Figure 1.4 Combined redox couples for catalytic oxidation of methane by O

2

....

Figure 1.5 Radical-initiated oxidation of methane by K

2

S

2

O

8

.

Figure 1.6 Cu(OAc)

2

-catalyzed methane oxidation.

Figure 1.7 Functionalization of methane by iodate/chloride system.

Figure 1.8 Proposed mechanism of the radical formation and carboxylation of ...

Figure 1.9 Proposed mechanism for the oxidative condensation of two methane ...

Figure 1.10 Yb(OAc)

3

-catalyzed carboxylation of methane to acetic acid.

Figure 1.11 Electrophilic initiator triggered direct sulfonation of methane....

Figure 1.12 Catalyst-controlled selectivity in the C–H borylation of methane...

Figure 1.13 Iridium-catalyzed borylation of methane [95].

Figure 1.14 Cerium-catalyzed amination of methane under ambient temperature....

Figure 1.15 Selective transformation of methane to aminated products by Tl(I...

Figure 1.16 Silver-catalyzed C—C bond formation between methane and ethyl di...

Figure 1.17 Decatungstate photocatalyst in flow enables the alkylation of me...

Figure 1.18 Ethane formation from palladium(II) complexes.

Chapter 2

Scheme 2.1 The applications of methanol as reagents in organic synthesis.

Scheme 2.2 Borrowing hydrogen (BH) methylation process using methanol.

Scheme 2.3 Rhodium-catalyzed methylation of ketones with methanol.

Scheme 2.4 Iridium-catalyzed α-methylation of ketones with methanol.

Scheme 2.5 Ir–NHC complex catalyzed α-methylation of ketones with methanol....

Scheme 2.6 Iridium-catalyzed methylation and double alkylation of ketones....

Scheme 2.7 Ruthenium-catalyzed methylation of ketones, alcohols, nitriles, a...

Scheme 2.8 Cobalt-catalyzed methylation of ketones with methanol.

Scheme 2.9 Manganese-catalyzed α-methylation of ketones with methanol.

Scheme 2.10 Manganese-catalyzed methylation and trideuteromethylation of ket...

Scheme 2.11 Iron-catalyzed methylation of ketones with methanol.

Scheme 2.12 Pd@sPS-N-catalyzed α-dimethylation and cross methyl alkylation o...

Scheme 2.13 Ni/SiO

2

-Al

2

O

3

-catalyzed methylation of ketones with methanol....

Scheme 2.14 Iridium-catalyzed α-methylation of α-aryl esters with methanol....

Scheme 2.15 Ruthenium-catalyzed methylation of 2-arylethanols with methanol....

Scheme 2.16 Plausible reaction mechanism.

Scheme 2.17 Ruthenium-catalyzed β-methylation of alcohols with methanol.

Scheme 2.18 The DMF-stabilized iridium nanoclusters catalyzed methylation of...

Scheme 2.19 Methylation of (bio)alcohols with methanol catalyzed by iridium ...

Scheme 2.20 Heterogeneous Pt/C-catalyzed methylation of alcohols, ketones, a...

Scheme 2.21 Iron-catalyzed β-C(sp

3

)-methylation of alcohols with methanol....

Scheme 2.22 Manganese-catalyzed β-methylation of alcohols with methanol.

Scheme 2.23 Ru-catalyzed aminomethylation and methylation of phenol derivati...

Scheme 2.24 Iridium-catalyzed

N

-monomethylation of aromatic primary amines....

Scheme 2.25 Site-specific N-methylation of peptides on-resin under Mitsunobu...

Scheme 2.26 Ruthenium-catalyzed

N

-methylation of amines with methanol.

Scheme 2.27 Ag/TiO

2

-catalyzed N-methylation of amines with methanol.

Scheme 2.28 Manganese-catalyzed N-methylation of primary anilines with metha...

Scheme 2.29 Manganese-catalyzed N-methylation of primary anilines with metha...

Scheme 2.30 Cp*Ir complex-catalyzed N-methylation of amines with methanol....

Scheme 2.31 Cobalt-catalyzed methylation of amines with methanol.

Scheme 2.32 Ru-catalyzed transformation of nitro compounds into N-methylated...

Scheme 2.33 Ruthenium-catalyzed synthesis of mono- and di-methylated amines....

Scheme 2.34 Ruthenium-catalyzed selective monomethylation of amines with met...

Scheme 2.35 Iron-catalyzed N-methylation of amines with methanol.

Scheme 2.36 Palladium-catalyzed N-methylation of nitroarenes with methanol....

Scheme 2.37 Palladium-catalyzed N-methylation of nitroarenes and amines with...

Scheme 2.38 Ruthenium-catalyzed N

-

methylation of amide from aldoximes ...

Scheme 2.39 TiCl

3

/TBHP-mediated radical hydroxymethylation of imines with me...

Scheme 2.40 Iridium-catalyzed hydroxymethylation of allenes with methanol....

Scheme 2.41 Iridium-catalyzed C−H hydroxymethylation of heteroarenes with me...

Scheme 2.42 Iridium-catalyzed enantioselective C−C coupling of 2-substituted...

Scheme 2.43 Na

2

S

2

O

8

-mediated hydroxymethylation of quinolines with methanol....

Scheme 2.44 Visible-light-mediated α-hydroxymethylation of ketones with meth...

Scheme 2.45 Ruthenium-catalyzed N-formylation of amines by methanol activati...

Scheme 2.46 AuNPore-catalyzed N-formylation of amines with methanol.

Scheme 2.47 Ru-catalyzed N-formylation of nitriles and amines using methanol...

Scheme 2.48 Ruthenium-catalyzed urea synthesis from methanol and amine.

Scheme 2.49 Manganese-catalyzed N-formylation of amines with methanol.

Scheme 2.50 Chromium-catalyzed N-formylation of amines with methanol.

Scheme 2.51 Copper-catalyzed N-formylation of amines with methanol.

Scheme 2.52 Pd(OAc)

2

-catalyzed C—H bond methoxylation of arenes with methano...

Scheme 2.53 Pd(OAc)

2

-catalyzed C—H bond methoxylation of benzamides and anil...

Scheme 2.54 Pd(OAc)

2

-catalyzed methoxylation of arylnitriles with methanol....

Scheme 2.55 Pd-catalyzed methoxylation of unactivated C(sp

3

)—H bonds.

Scheme 2.56 Pd(OAc)

2

-catalyzed methoxylation of unactivated C(sp

3

)—H bonds....

Scheme 2.57 Copper-catalyzed methoxylation of unactivated (hetero)aryl C—H b...

Scheme 2.58 Palladium-catalyzed methoxylation of 2-aryl-1,2,3-triazoles with...

Scheme 2.59 Palladium-catalyzed double C(sp

3

)−H methoxylation with methanol....

Scheme 2.60 Ru-catalyzed ring-opening reactions of 7-oxabenzonorbornadienes ...

Scheme 2.61 Methanol facilitated synthesis of methoxy substituted 1,3-diazep...

Scheme 2.62 Pd-catalyzed methoxycarbonylation of alkenes.

Scheme 2.63 Sodium iodide-catalyzed direct α-methoxylation of ketones with m...

Scheme 2.64 Pd/C-catalyzed benzylic methoxylation with methanol.

Scheme 2.65 Palladium-catalyzed oxidation-methoxylation of

N

-Boc indoles wit...

Scheme 2.66 NBS-mediated 1,3-bromoetherification of unactivated cyclopropane...

Scheme 2.67 Pd-catalyzed three-component coupling reaction of

o

-bromobenzald...

Scheme 2.68 Copper-catalyzed benzylic C–H coupling reactions with methanol....

Scheme 2.69 Palladium-catalyzed coupling reactions of aryl bromides and chlo...

Scheme 2.70 Palladium-catalyzed synthesis of methyl aryl ethers with methano...

Scheme 2.71 Iridium-catalyzed synthesis of 3,3′-bisindolylmethanes with meth...

Scheme 2.72 Cu-PMOs-promoted synthesis of benzimidazoles in supercritical me...

Scheme 2.73 Iridium-catalyzed synthesis of quinazolinones with methanol.

Scheme 2.74 Copper-catalyzed synthesis of quinazolines with methanol.

Scheme 2.75 Manganese-catalyzed aminomethylation of aromatic compounds with ...

Scheme 2.76 Cobalt-catalyzed α-methoxymethylation and aminomethylation of ke...

Scheme 2.77 Oxidative sulfonamidomethylation of imidazopyridines with methan...

Chapter 3

Figure 3.1 MTO process linking petrochemical industry and coal chemical indu...

Figure 3.2 MTO technology development.

Figure 3.3 Catalyst and technology development of the DMTO process.

Figure 3.4 The framework (a) and pore structures (b) of MFI.

Figure 3.5 The cavity structure (a) and 8-MR pore opening size (b) of CHA.

Figure 3.6 Molecular sieves with 8-MR and cavity structure.

Figure 3.7 Direct mechanisms for the conversion of methanol/dimethyl ether t...

Figure 3.8 First C—C bond formation in MTH through coupling between nucleoph...

Figure 3.9 Temperature-programmed surface reaction of MeOH on HZSM-5 under (...

Figure 3.10 (a) Route for the formation of the first C—C bond. (b) IR spectr...

Figure 3.11 (a) C-OCH

3

activation process assisted by an OH group of the CH

3

Figure 3.12 (a)

13

C MAS NMR spectra of trapped products obtained from reacti...

Figure 3.13 (a)–(c) Proposed reaction routes for the formation of C—C bond-c...

Figure 3.14 (a)–(e) ssNMR spectra of methanol, methoxy, and acetyl species i...

Figure 3.15 (a) Ex situ

13

C CP/MAS NMR spectra of the HZSM-5 catalyst after

Figure 3.16 Product distribution in methanol conversion over H-ZSM-5 at 492 ...

Figure 3.17 Three-stage MTH induction reaction mechanism.

Figure 3.18 Olefin methylation cracking mechanism proposed by Dessau and Lap...

Figure 3.19 The hydrocarbon pool mechanism proposed by Dahl and Kolboe.

Figure 3.20 Supramolecular concept proposed by Haw and coworkers.

Figure 3.21 Paring mechanism and side-chain methylation mechanism.

Figure 3.22 Side-chain methylation mechanism for olefin generation over DNL-...

Figure 3.23 Catalytic cycles of the paring and side-chain reaction mechanism...

Figure 3.24 The results after

12

C/

13

C-methanol switch over H-ZSM-5.

Figure 3.25 Dual cycle mechanism for MTO over H-ZSM-5.

Figure 3.26 The traditional dual cycles and the cyclopentadienes-based cycle...

Figure 3.27 Cyclopentadienes-based cycle starting from PMCP

+

for ethene ...

Figure 3.28 Formation and evolution of various initial HCP intermediates in ...

Figure 3.29 2D

13

C-

13

C MAS solid-state NMR spectra.

Figure 3.30 Proposed reaction pathways of the methyl-acetate-to-hydrocarbon ...

Figure 3.31

13

C MAS NMR spectra of H-SSZ-13 and H-Beta zeolites on the react...

Figure 3.32 (a) GC–MS chromatograms and (b) isotopic distribution of the org...

Figure 3.33 Illustration of proposed reaction network of MTO process.

Figure 3.34 (a)–(c) Confocal fluorescence intensity profiles of the H-ZSM-5 ...

Figure 3.35 (a)–(e) Confined coke after methanol conversion at different tem...

Figure 3.36 (a) Bright field images and (b) confocal fluorescence microscopy...

Figure 3.37 Capture and identification of the intermediates by GC–MS after m...

Figure 3.38 The possible routes of coke precursor evolution over H-SAPO-34....

Figure 3.39 (a)–(e) The structural identification of PAHs.

Figure 3.40 Flow diagram of DMTO industrial test plant.

Figure 3.41 Typical results obtained from DMTO Demonstration Unit plant.

Figure 3.42 DMTO commercial unit in Shenhua Baotou.

Figure 3.43 Scheme of DMTO-II process.

Chapter 4

Scheme 4.1

Hemilabile

behavior of P–O donor ligand (opening and closing mech...

Scheme 4.2 Chelate formation of N → O donor ligand.

Scheme 4.3 Development of supported Rh-catalyst and carbonylation of methano...

Figure 4.1 Metal–CO bonding and energy levels of molecular orbitals diagram ...

Figure 4.2 Catalytic cycle for Co-complex catalyzed BASF process for carbony...

Figure 4.3 Catalytic cycle for carbonylation reaction catalyzed by Rh-comple...

Figure 4.4 Catalytic cycle for WGS reaction catalyzed by [Rh(CO)

2

I

2

]

−

....

Figure 4.5 Catalytic cycle for carbonylation of methanol catalyzed by Ir-com...

Figure 4.6 Carbonylation reaction catalyzed by Ni-complex.

Figure 4.7 Molecular structure of the complex

trans

-[Rh(CO)Cl(2-Ph

2

PC

6

H

4

COOM...

Figure 4.8 Oxidative addition and migration insertion of the complexes

1

and...

Figure 4.9 Ligand structures of xantphos, DPEphos, and oxide derivatives....

Figure 4.10 Influence of phosphorus and oxygen donor diphosphine ligands in ...

Figure 4.11 Structure of [Rh

4

(CO)

8

Cl

4

(P′P

3

X

4

)].

Figure 4.12 X-ray structure of [RhCl(CO){

η

2

-P,Se-Ph

2

PN(CH

3

)P(Se)Ph

2

}]....

Figure 4.13 Pyridine-based rhodium complexes [Rh(CO)

2

ClL] catalyzed carbonyl...

Figure 4.14 Structures of N → O ligands.

Chapter 5

Scheme 5.1 Industrial production of formaldehyde.

Scheme 5.2 (a)–(c) Available sources of formaldehyde monomers.

Scheme 5.3 Formaldehyde as C

1

synthon in selected named reactions.

Scheme 5.4 Baeyer diarylmethane synthesis.

Scheme 5.5 Aqueous sulfuric acid catalyzed Baeyer synthesis.

Scheme 5.6

Scheme 5.7 In-catalyzed synthesis of diarylmethanes using CFA.

Scheme 5.8 FeCl

3

-catalyzed formation of diarylmethanes with PFA.

Scheme 5.9 Ionic liquid as the catalyst for diarylmethane synthesis.

Scheme 5.10 Proline-catalyzed formation of unsymmetrical diarylmethanes.

Scheme 5.11

Scheme 5.12 Preparation of giant calixarenes.

Scheme 5.13 Cobalt-catalyzed homologation of dibenzoylmethanes with PFA.

Scheme 5.14 Plausible reaction mechanism.

Scheme 5.15 Synthesis of cyclopropanones from aliphatic aldehydes and formal...

Scheme 5.16 Cascade Heck–Aldol–Heck reaction via hybrid palladium-organo cat...

Scheme 5.17

Scheme 5.18 Formaldehyde in Mannich reactions.

Scheme 5.19 First example of asymmetric Mannich reaction.

Scheme 5.20 Asymmetric Mannich reaction using AFA.

Scheme 5.21 CuI-catalyzed Mannich-type reaction for propargyl amine synthesi...

Scheme 5.22 CuI-catalyzed formation of 3-(aminomethyl)isoquinolones.

Scheme 5.23 CuCl-catalyzed formation of 3-(aminomethyl)isoquinoline-fused ri...

Scheme 5.24 CuBr-catalyzed synthesis of 2-(aminomethyl)indoles.

Scheme 5.25 Three-component reaction between amino alcohols, PFA, and propio...

Scheme 5.26 Three-component reaction between amino alcohols, AFA, and propio...

Scheme 5.27 Decarboxylative coupling to synthesize allyl amines.

Scheme 5.28 Pd-catalyzed vinylation reaction of aminals to form allylic amin...

Scheme 5.29 PFA as a “co-catalyst” in Pd-catalyzed hydroaminocarbonylation o...

Scheme 5.30 Cobalt-catalyzed synthesis of tertiary benzyl amines.

Scheme 5.31 Iodine-catalyzed synthesis of allylic amines.

Scheme 5.32 Example of Pictet–Spengler isoquinoline synthesis using AFA.

Scheme 5.33

Scheme 5.34

Scheme 5.35

Scheme 5.36

Scheme 5.37

Scheme 5.38

Scheme 5.39

Scheme 5.40 CuI-catalyzed synthesis of propargyl alcohols.

Scheme 5.41 Zn-promoted hydroxymethylation of base-sensitive alkynes.

Scheme 5.42 Blanc chloromethylation.

Scheme 5.43 Bromomethylation with CFA and HBr.

Scheme 5.44 Bromomethylation with PFA and HBr.

Scheme 5.45

Scheme 5.46 Bromomethylation of mesitylene using PFA and KBr.

Scheme 5.47 Synthesis of terminal allenes from alkynes and PFA.

Scheme 5.48 Modified procedure of terminal allenes synthesis.

Scheme 5.49 Synthesis of enantiopure allenes from propargyl alcohols.

Scheme 5.50 γ-Methylenation of α,β-unsaturated aldehydes using AFA.

Scheme 5.51

Scheme 5.52

Scheme 5.53

Scheme 5.54

Scheme 5.55

Scheme 5.56

Scheme 5.57

Scheme 5.58

Scheme 5.59 Use of (a) AFA and (b) PFA as protecting groups.

Scheme 5.60

Scheme 5.61 Formaldehyde condensed with two amino groups.

Scheme 5.62 Reaction of nitramine and paraformaldehyde.

Scheme 5.63 Formation of hexahydrotriazines from anilines and paraformaldehy...

Scheme 5.64 Paraformaldehyde for the synthesis of Törger's base.

Scheme 5.65 Synthesis of

N

-acyl-5-oxazolidones.

Scheme 5.66 Synthesis of naphtho-bis[1,3]oxazines.

Scheme 5.67 Formaldehyde used to link nitrogen–phosphorous atom.

Scheme 5.68

Scheme 5.69

Scheme 5.70 Synthesis of 1,3-dioxanes from formaldehyde.

Scheme 5.71 Pd-catalyzed formation of chiral quaternary carbon centers.

Scheme 5.72

Scheme 5.73 C–C coupling between dihydroxyacetone and formaldehyde.

Scheme 5.74 Formaldehyde for Aldol reactions.

Scheme 5.75 Gold-catalyzed asymmetric Aldol reaction.

Scheme 5.76 Rh-catalyzed asymmetric hydroxymethylation of 2-cyanopropionates...

Scheme 5.77 Fe-catalyzed hydroxymethylation of β-dicarbonyl compounds.

Scheme 5.78 Metal-containing ionic liquids as catalysts for hydroxymethylati...

Scheme 5.79 Nickel-catalyzed hydroxymethylation of β-keto esters.

Scheme 5.80 Water-compatible Lewis acid catalyst for the hydroxymethylation ...

Scheme 5.81 Zn-catalyzed hydroxymethylation of ketones in EtOH/H

2

O.

Scheme 5.82 First example of organocatalyzed hydroxymethylation of ketones a...

Scheme 5.83 Proline-derived tetrazole as the catalyst for hydroxymethylation...

Scheme 5.84

L

-Threonine-catalyzed asymmetric hydroxymethylation of cyclic ke...

Scheme 5.85 Direct enantioselective organocatalyzed hydroxymethylation of al...

Scheme 5.86 Asymmetric hydroxymethylation of oxindoles by bifunctional thiou...

Scheme 5.87 NHC-catalyzed hydroxymethylation of aldehydes.

Scheme 5.88 Cupreidine-catalyzed hydroxymethylation of α-substituted nitroac...

Scheme 5.89 Hydroxymethylation of α-substituted nitroacetates.

Scheme 5.90 Vanadium-promoted pinacol cross-coupling.

Scheme 5.91 Prins reaction using paraformaldehyde.

Scheme 5.92 Pins reaction leading to 1,3-dioxanes.

Scheme 5.93

Scheme 5.94

Scheme 5.95

Scheme 5.96 Carbonyl-ene reactions between alkenes and formaldehyde.

Scheme 5.97

Scheme 5.98

Scheme 5.99

Scheme 5.100

Scheme 5.101

Scheme 5.102

Scheme 5.103

Scheme 5.104 Asymmetric carbonyl-ene reaction.

Scheme 5.105

Scheme 5.106

Scheme 5.107 Selected examples of other MBH products.

Scheme 5.108 Interrupted Morita–Baylis–Hillman reaction.

Scheme 5.109 Fe-catalyzed hydroxymethylation of allyl alcohol.

Scheme 5.110 Ru-catalyzed reductive hydroxymethylation of allenes.

Scheme 5.111 Mechanism for Ru-catalyzed reductive hydroxymethylation of alle...

Scheme 5.112 Ru-catalyzed reductive hydroxymethylation of CF

3

-bearing allene...

Scheme 5.113 Ru-catalyzed reductive hydroxymethylation of 1,3-butadienes by ...

Scheme 5.114 Mechanism for Ru-catalyzed reductive hydroxymethylation.

Scheme 5.115 Ni-catalyzed selective reductive hydroxymethylation of 1,3-buta...

Scheme 5.116 Mechanistic proposals.

Scheme 5.117 Regiodivergent reductive hydroxymethylation of alkynes catalyze...

Scheme 5.118 Mechanism for Ru- and Ni-catalyzed reductive hydroxymethylation...

Scheme 5.119 Hydroxymethylation of organomagnesium and organolithium.

Scheme 5.120 (a)–(d) Reaction of organoboranes with formaldehyde.

Scheme 5.121 Pd-catalyzed hydroxymethylation of phenylboronic acids.

Scheme 5.122

Scheme 5.123

Scheme 5.124

Scheme 5.125

Scheme 5.126

Scheme 5.127 Ru-catalyzed hydroxymethylation of C—H bonds.

Scheme 5.128

Scheme 5.129

Scheme 5.130 Rh-catalyzed carbonylation of

N

-tosyl (2-bromobenzylamine).

Scheme 5.131 Rh-catalyzed carbonylation of

N

-tosyl (2-bromobenzylamine).

Scheme 5.132

Scheme 5.133

Scheme 5.134 Pd-catalyzed reductive and alkoxycarbonylation of aryl bromides...

Scheme 5.135 Pd-catalyzed carbonylative synthesis of benzoxazinones using PF...

Scheme 5.136

Scheme 5.137 Pd-catalyzed carbonylative synthesis of phthalazinones using PF...

Scheme 5.138

Scheme 5.139 Ru cluster catalyzed carbonylation of cyclohexenes.

Scheme 5.140 Ru-catalyzed alkoxylcarbonylation of alkenes using PFA.

Scheme 5.141

Scheme 5.142 Rh-catalyzed cyclohydrocarbonylation reactions of alkynes with ...

Scheme 5.143

Scheme 5.144 Rh-catalyzed carbonylative arylation of alkynes with boronic ac...

Scheme 5.145

Scheme 5.146 Rh-catalyzed asymmetric Pauson–Khand-type reactions.

Scheme 5.147

Scheme 5.148 Rh-catalyzed hydroformylation of alkenes using PFA.

Scheme 5.149 Rh-catalyzed hydroformylations using PFA as CO source.

Scheme 5.150 Rh-catalyzed hydroformylation using PFA as CO source.

Scheme 5.151 Rh-catalyzed hydroformylation of 1-alkenes using PFA.

Scheme 5.152 Rh-catalyzed hydroformylation using PFA under microwave irradia...

Scheme 5.153 Rh-catalyzed asymmetric hydroformylation using PFA as syngas eq...

Scheme 5.154

Scheme 5.155 Rh-catalyzed hydroformylation using PFA under H

2

.

Scheme 5.156 Synthesis of symmetric ketones.

Scheme 5.157 Oxidation states of carbon in simple C

1

molecules.

Scheme 5.158 Pd-catalyzed reduction of aryl bromides and iodides with PFA....

Scheme 5.159 Ru-catalyzed conjugated hydrogenation of α,β-enones.

Scheme 5.160 Fe-catalyzed reduction of aldehydes by PFA and H

2

O.

Scheme 5.161 Ru-catalyzed oxidation of alcohols using PFA as oxidant.

Scheme 5.162

Scheme 5.163 Rh-catalyzed α-methylation of ketones and amines using formalin...

Scheme 5.164 Co-catalyzed methylation of amine with PFA under CO pressure....

Scheme 5.165 Methylation of amines by formalin under transition-metal-free c...

Scheme 5.166

Scheme 5.167 Ru-catalyzed methylation using PFA.

Scheme 5.168 Trioxane as a methylation reagent.

Scheme 5.169 Ir-catalyzed N-formylation of amines using PFA.

Scheme 5.170 Ru-catalyzed N-formylation of lactams.

Scheme 5.171 Fe-catalyzed O-formylation of alcohols.

Scheme 5.172 Synthesis of osmium and ruthenium complexes with formaldehyde....

Scheme 5.173

Scheme 5.174 Reaction of vanadocene with paraformaldehyde.

Scheme 5.175 Reaction of PbO with aqueous formaldehyde.

Scheme 5.176 Formaldehyde as ligand for Pd-catalyzed cross-couplings.

Chapter 6

Scheme 6.1 Formic acid in chemical synthesis.

Scheme 6.2 Pd-catalyzed carbonylative Sonogashira and Suzuki coupling reacti...

Scheme 6.3 Pd-catalyzed carbonylative synthesis of esters and amides.

Scheme 6.4 Pd-catalyzed carbonylative synthesis of heterocycles.

Scheme 6.5 Pd-catalyzed carbonylative synthesis of pyrrolidin-2-one and imid...

Scheme 6.6 Pd-catalyzed carbonylative synthesis of aromatic aldehydes.

Scheme 6.7 Pd-catalyzed hydroformylation of olefins.

Scheme 6.8 Rh- and Pd-catalyzed carbonylative synthesis of ketones, amides, ...

Scheme 6.9 Formylation of amines with formic acid.

Scheme 6.10 Pd-catalyzed carboxylative synthesis of acids from aryl and viny...

Scheme 6.11 Pd-catalyzed carboxylative synthesis of acid with formic acid un...

Scheme 6.12 Pd-catalyzed carboxylation of aromatic C(sp

2

)—H bonds.

Scheme 6.13 Ir-catalyzed hydrocarboxylation of alkenes.

Scheme 6.14 Pd-catalyzed hydrocarboxylation of olefins.

Scheme 6.15 Pd-catalyzed hydrocarboxylation of olefins for the synthesis of ...

Scheme 6.16 Pd- and Ni-catalyzed hydrocarboxylation of alkynes.

Scheme 6.17 Ni-catalyzed hydrocarboxylation of internal alkynes.

Scheme 6.18 Pd- and Ir-catalyzed hydrogen transfer reduction of olefins with...

Scheme 6.19 Palladium carbene catalyzed semi-hydrogenation of alkynes.

Scheme 6.20 Pd-catalyzed semi-hydrogenation of alkynes.

Scheme 6.21 Au-catalyzed transfer semi-hydrogenation of alkynes to

Z

-olefins...

Scheme 6.22 Ru-catalyzed semi-hydrogenation and reductive hydration of alkyn...

Scheme 6.23 Fe- and Ni-catalyzed reductive semi-hydrogenation of alkynes....

Scheme 6.24 Rh- and Fe-catalyzed transfer hydrogenation aldehydes to alcohol...

Scheme 6.25 Pd- and Ir-catalyzed transfer hydrogenation of ketones.

Scheme 6.26 Rh- catalyzed asymmetric transfer hydrogenation ketones.

Scheme 6.27 Ru-catalyzed asymmetric transfer hydrogenation ketones.

Scheme 6.28 Various tethered-Ru catalysts for asymmetric transfer hydrogenat...

Scheme 6.29 Oxo-tethered-Ru-catalyzed asymmetric transfer hydrogenation.

Scheme 6.30 Pd-catalyzed reductive ring-opening hydrogenolysis of epoxides....

Scheme 6.31 Pd-catalyzed transfer hydrogenation of benzylic alcohols.

Scheme 6.32 Ru-catalyzed transfer hydrogenation of nitroarenes.

Scheme 6.33 Fe-, and Mo-catalyzed transfer hydrogenation of nitroarenes.

Scheme 6.34 Heterogeneous Co-, and Fe-catalyzed transfer hydrogenation of ni...

Scheme 6.35 Heterogeneous Co-catalyzed reductive annulation of 2-nitroaryl c...

Scheme 6.36 Ir-, and Ru-catalyzed transfer hydrogenation of imines.

Scheme 6.37 Co-catalyzed transfer hydrogenation of quinolines.

Scheme 6.38 Ir-catalyzed transfer hydrogenation of quinolines for the synthe...

Scheme 6.39 Ir-catalyzed synthesis of fused indoles through transfer hydroge...

Scheme 6.40 Pd/C-catalyzed transfer hydrogenation of aryl nitriles.

Scheme 6.41 Pt-catalyzed methylation of amines and imines.

Scheme 6.42 Ru-, and Cu-catalyzed methylation of amines.

Chapter 7

Figure 7.1 Procedure of synthesis of POL-PPh

3

and its performance in ethylen...

Figure 7.2 An industrial unit for an annual capacity of 50 000 tons of

n

-pro...

Figure 7.3 Preparation of Rh/CPOL-bp&P catalyst and its performance in prope...

Figure 7.4 (a) A path of the formation and transformation of the active spec...

Figure 7.5 (a) The structure of Xantphos-doped Rh/POPs-PPh

3

; (b) comparison ...

Figure 7.6 (a) Preparation of Poly-1, Poly-2, and Poly-3; (b) performance in...

Figure 7.7 (a) The scheme of Rh-POL-2BPY preparation; (b, c) N

2

sorption iso...

Figure 7.8 (a) The theoretical model of Rh-TPISP. (b, c) N

2

sorption isother...

Figure 7.9 (1) Preparation of 4-BINAP@POPs, 5-BINAP@POPs, and supported Ru c...

Figure 7.10 (a) Synthesis of POL-2V-P,N; (b) comparison of homogeneous and h...

Figure 7.11 (a) Designs of ligands for the selective Heck reaction and (b) r...

Figure 7.12 Scheme of PSIL(IMD)-1 and PSIL(IMD)-2 synthesis and stability of...

Chapter 8

Scheme 8.1 Transition metal-catalyzed hydrocarbonylation of unsaturated bond...

Scheme 8.2 Mechanism of cobalt-catalyzed propene hydroformylation.

Scheme 8.3 Cobalt-catalyzed hydroformylation.

Scheme 8.4 Hydroformylation mechanism involving 19e

−

catalyst species....

Scheme 8.5 The hydroformylation catalyzed by cationic Co(II) complex [HCo

II

(...

Scheme 8.6 Rh-catalyzed asymmetric hydroformylation with small bite-angle P-...

Scheme 8.7 Rh-catalyzed asymmetric hydroformylation of functionalized termin...

Scheme 8.8 Rh-catalyzed asymmetric hydroformylation with pyrrolyl-based phos...

Scheme 8.9 Rh-catalyzed asymmetric hydroformylation of vinyl acetate and all...

Scheme 8.10 Synthesis of enantioenriched aldehydes by asymmetric hydroformyl...

Scheme 8.11 Rhodium-catalyzed asymmetric hydroformylation of styrene.

Scheme 8.12 Asymmetric hydroformylation of vinyl heteroarenes.

Scheme 8.13 Asymmetric hydroformylation of 1,2-disubstituted alkenylsilanes....

Scheme 8.14 Rh-catalyzed anti-Markovnikov asymmetric hydroformylation of unf...

Scheme 8.15 Rhodium-catalyzed asymmetric anti-Markovnikov hydroformylation o...

Scheme 8.16 Asymmetric hydroformylation of heterocyclic 1,1-disubstituted ol...

Scheme 8.17 Rh-catalyzed asymmetric hydroformylation of 2,3-dihydrofuran.

Scheme 8.18 Immobilized bisdiazaphospholane catalysts for asymmetric hydrofo...

Scheme 8.19 Domino hydroformylation-enantioselective anti-Mannich reaction....

Scheme 8.20 The tandem process consisting of hydroformylation and acyloin co...

Scheme 8.21 Rhodium-catalyzed hydroformylation-reductive sulphonamidation.

Scheme 8.22 Selective conversion of

n

-alkanes to

n

-alcohols.

Scheme 8.23 Rhodium-catalyzed bis-hydroformylation of 1,3-butadiene.

Scheme 8.24 (

κ

2

-L)Rh(

η

3

-crotyl) and (

κ

2

-L)Rh(

η

3

-crotyl)(...

Scheme 8.25 Rh-catalyzed hydroformylation of 1,3-butadiene with bisphosphite...

Scheme 8.26 Rhodium-catalyzed hydroformylation of 1,3-butadiene to adipic al...

Scheme 8.27 Rh-catalyzed hydroformylation of 1,3-butadiene.

Scheme 8.28 Rh/DIOP-catalyzed 1,3-butadiene hydroformylation products.

Scheme 8.29 Rh-catalyzed hydroformylation of 1,3-butadiene in CO

2

-expanded m...

Scheme 8.30 Butadiene hydroformylation to adipaldehyde with Rh-based catalys...

Scheme 8.31 Rhodium-complex-catalyzed hydroformylation of olefins with CO

2

a...

Scheme 8.32 Ruthenium-catalyzed isomerization-hydroformylation-reduction of ...

Scheme 8.33 Ruthenium-catalyzed domino hydroformylation-reduction of alkenes...

Scheme 8.34 Ruthenium-catalyzed hydroaminomethylation of olefins.

Scheme 8.35 Ruthenium-catalyzed synthesis of tertiary amine.

Scheme 8.36 Ruthenium-catalyzed domino water-gas shift-hydroaminomethylation...

Scheme 8.37 Reaction network in the hydroformylation of 1-octene.

Scheme 8.38 Hydroformylation of 3,3-dimethyl-1-butene.

Scheme 8.39 Ruthenium-catalyzed RWGS-hydroformylation-reduction of olefins w...

Scheme 8.40 Iron catalyzed hydroformylation of alkenes.

Scheme 8.41 Osmium-catalyzed hydroformylation reactions.

Scheme 8.42 Iridium-catalyzed hydroformylation of olefins.

Scheme 8.43 Iridium catalysts for the hydroformylation of olefins.

Scheme 8.44 Hydroformylation of 1-octene.

Scheme 8.45 IrCl

3

·3H

2

O-catalyzed hydroformylation-acetalization.

Scheme 8.46 Ir(I)-complex catalyzed hydroaminomethylation of olefins.

Scheme 8.47 Organo-photoredox-catalyzed hydroformylation of styrenes.

Scheme 8.48 Palladium-catalyzed tunable selective aminocarbonylation of 1,3-...

Scheme 8.49 Palladium-catalyzed alkoxycarbonylation of conjugated dienes....

Scheme 8.50 Pd-catalyzed selective hydrocarbonylation of

gem

-difluoroalkenes...

Scheme 8.51 Palladium-catalyzed carbonylation of olefins to ketones.

Scheme 8.52 Pd-catalyzed methoxycarbonylation of styrene.

Scheme 8.53 Palladium-catalyzed Markovnikov alkoxycarbonylation of alkenes....

Scheme 8.54 Palladium-catalyzed allene alkoxycarbonylation.

Scheme 8.55 Palladium-catalyzed methoxycarbonylation of tetramethylethylene....

Scheme 8.56 Palladium-catalyzed alkoxycarbonylation of bulk industrial olefi...

Scheme 8.57 Proposed mechanism of Pd-catalyzed olefin methoxycarbonylation....

Scheme 8.58 Regioselective Pd-catalyzed methoxycarbonylation of alkenes.

Scheme 8.59 Selective generation of CO from formic acid for alkene alkoxycar...

Scheme 8.60 Pd-catalyzed alkoxycarbonylation of 1-octene with

13

C-PFA reacti...

Scheme 8.61 Synthesis of carboxylic acids by palladium-catalyzed hydroxycarb...

Scheme 8.62 Palladium-catalyzed bis-alkoxycarbonylation of 1,3-dienes.

Scheme 8.63 Pd-catalyzed regioselective alkoxycarbonylation of 1-alkenes....

Scheme 8.64 Pd-catalyzed aminocarbonylation of styrenes with aminophenols....

Scheme 8.65 Regioselective alkoxycarbonylation of allyl phenyl ethers cataly...

Scheme 8.66 Palladium-catalyzed aminocarbonylation with the aliphatic amine ...

Scheme 8.67 Palladium-catalyzed intramolecular aminocarbonylation reaction....

Scheme 8.68 Catalytic regioselective aminocarbonylation of alkenes.

Scheme 8.69 Palladium-catalyzed regiodivergent aminocarbonylation of alkenes...

Scheme 8.70 Catalytic hydrocarbonylative C-N coupling of alkenes with amides...

Scheme 8.71 Palladium-catalyzed hydrocarbonylative cyclization.

Scheme 8.72 Palladium-catalyzed hydrocarbonylative cyclization of 1,5-dienes...

Scheme 8.73 Reactive chelating-group-assisted Pd-catalyzed hydrocarbonylativ...

Scheme 8.74 Catalytic hydroesterificative copolymerization of vinyl benzyl a...

Scheme 8.75 Routes to acrylate esters from alkyl lactates.

Scheme 8.76 Pd-catalyzed alkoxycarbonylation of alkenes with different ligan...

Scheme 8.77 Pd-catalyzed hydrocarboxylation of olefins.

Scheme 8.78 Pd-catalyzed hydrocarbonylation of alkenes.

Scheme 8.79 Pd-phosphine-catalyzed cascade transformation of HMF to ester pr...

Scheme 8.80 Palladium-catalyzed hydroesterification of olefins in the presen...

Scheme 8.81 Brønsted acid ionic liquid for the continuous gas-phase ethylene...

Scheme 8.82 Palladium-catalyzed enantioselective hydrocarbonylation of alken...

Scheme 8.83 Palladium-catalyzed enantioselective hydroesterification of alke...

Scheme 8.84 Palladium-catalyzed regio- and enantioselective hydroesterificat...

Scheme 8.85 Palladium-catalyzed enantioselective hydrothiocarbonylation of s...

Scheme 8.86 Asymmetric Markovnikov hydroaminocarbonylation of alkenes.

Scheme 8.87 Pd/(2-Py)PPh

2

-catalyzed branched-selective methoxycarbonylation ...

Scheme 8.88 Mechanism of homogeneous methyl methacrylate formation.

Scheme 8.89 Proposed π-allyl palladium intermediate in the alkoxycarbonylati...

Scheme 8.90 Propyne hydromethoxyoxcarbonylation.

Scheme 8.91 Palladium-catalyzed hydrocarboxylation of alkynes.

Scheme 8.92 Pd-catalyzed bis-alkoxycarbonylation of alkynes.

Scheme 8.93 Bis-alkoxycarbonylation of alkynes with Pd/Xantphos/Al(OTf)

3

bif...

Scheme 8.94 Palladium-catalyzed alkoxycarbonylation of alkynes.

Scheme 8.95 Palladium-catalyzed carbonylative synthesis of 1,3-enynes.

Scheme 8.96 Palladium-catalyzed intramolecular hydroaminocarbonylation of am...

Scheme 8.97 Palladium-catalyzed hydroaminocarbonylation of alkynes.

Scheme 8.98 Pd-catalyzed selective alkoxycarbonylation of alkynes.

Scheme 8.99 Pd-catalyzed alkoxycarbonylation of alkynes promoted by H

2

O addi...

Scheme 8.100 Pd-catalyzed alkoxycarbonylation of alkynols to β-lactone.

Scheme 8.101 Palladium-catalyzed carbonylation of

s

-and

t

-alcohols.

Scheme 8.102 Pd-catalyzed alkoxycarbonylation of secondary benzylic methyl e...

Scheme 8.103 Palladium-catalyzed hydroxycarbonylation of pentenoic acids.

Scheme 8.104 Nickel-catalyzed hydrocarboxylation of alkynes with formic acid...

Scheme 8.105 Nickel-catalyzed regio- and stereoselective hydrocarboxylation ...

Scheme 8.106 Ni-catalyzed carboxylation of diene feedstocks with CO

2

.

Scheme 8.107 Ruthenium-catalyzed alkoxycarbonylation of alkenes with CO

2

....

Scheme 8.108 Ruthenium-catalyzed methoxycarbonylation reaction.

Scheme 8.109 Ruthenium-catalyzed hydroesterification of alkenes assisted by ...

Scheme 8.110 Ruthenium-catalyzed hydroesterification of alkenes.

Scheme 8.111 Pt-catalyzed alkoxycarbonylation of alkenes.

Chapter 9

Scheme 9.1 Simplified mechanism of a typical palladium-catalyzed carbonylati...

Scheme 9.2 Carbonylation of pseudohalides.

Scheme 9.3 Pd-Josiphos-catalyzed carbonylation of aryl sulfonates.

Scheme 9.4 Carbonylation catalyzed by Rh catalysts.

Scheme 9.5 Chemoselective carbonylation of aminophenols with iodoarenes.

Scheme 9.6 Chemoselective carbonylation of bromoaryl triflates.

Scheme 9.7 Mono or double aminocarbonylation without stirring or under stirr...

Scheme 9.8 Carbonylation catalyzed by Fe, Co, Ni, Cu, and Mn.

Scheme 9.9 The mechanism of high-energy light-induced palladium-catalyzed ca...

Scheme 9.10 UV-induced palladium-catalyzed Suzuki carbonylation.

Scheme 9.11 Photo-induced cobalt-catalyzed carbonylations.

Scheme 9.12 UV-light-assisted metal-free aminocarbonylation.

Scheme 9.13 Visible-light irradiated carbonylation of arenediazonium salts....

Scheme 9.14 Photoinitiated radical carbonylations catalyzed by Ir polypyridy...

Scheme 9.15 Visible-light-induced photoredox carbonylations to synthesize ar...

Scheme 9.16 Radical Carbonylations of C(sp

2

)—X bonds by AIBN/Bu

3

SnH.

Scheme 9.17 Base-promoted alkoxycarbonylation of aryl diazonium salts.

Scheme 9.18 Phosphite-catalyzed alkoxycarbonylation of aryl diazonium salts....

Scheme 9.19 Pd-catalyzed carbonylative synthesis of aurones with formic acid...

Scheme 9.20 Pd-catalyzed aminocarbonylation using DMF as the CO source.

Scheme 9.21 Rh-catalyzed carbonylation of

N

-tosyl(2-bromo-benzylamine) using...

Scheme 9.22 The applications of TFBen as a CO source in carbonylation.

Scheme 9.23 Aminocarbonylation of aromatic halides using carbamoylsilane as ...

Scheme 9.24 Pd-catalyzed hydroxycarbonylation using formate anion as CO sour...

Scheme 9.25 The applications of CO

2

as a CO source in carbonylation.

Scheme 9.26 The applications of isocyanides as a CO source in carbonylation....

Scheme 9.27 Ex situ CO-generation.

Scheme 9.28 Carbonylative reactions terminated by C(sp

2

)–H activation.

Scheme 9.29 Chlorocarbonylation of aryl halides.

Scheme 9.30 Uncommon nucleophiles to capture acyl palladium complex.

Scheme 9.31 Two types of intramolecular domino carbonylations.

Scheme 9.32 Mo(CO)

6

as a CO substitute to produce indanones.

Scheme 9.33 Carbopalladation producing five-membered rings.

Scheme 9.34 Four-component synthesis of 2-aryl-4-aminoquinolines and analogu...

Scheme 9.35 Synthesis of pyrazoles and isoxazoles.

Scheme 9.36 Four-component synthesis of thiochromenones with

o

-fluoroiodoben...

Scheme 9.37 One-pot carbonylative Sonogashira coupling in tandem with double...

Scheme 9.38 Palladium-catalyzed carbonylative cascade reactions of allenes....

Scheme 9.39 The mechanism of continuous carbonylation for two adjacent carbo...

Scheme 9.40 Palladium-catalyzed continuous double carbonylation of aryl/alke...

Scheme 9.41 Synthesis of α-keto esters by the double carbonylation.

Scheme 9.42 Double isocyanide insertion for diketones.

Scheme 9.43 The synthesis of N-substituted phthalimides using dihaloarenes w...

Scheme 9.44 The first case of asymmetric carbonylations of C(sp

2

)–X bonds....

Scheme 9.45 Pd(0)-catalyzed asymmetric carbonylation to synthesize planar ch...

Scheme 9.46 Pd-catalyzed asymmetric tandem Heck carbonylation and desymmetri...

Scheme 9.47 Enantioselective Heck carbonylations.

Scheme 9.48 Enantioselective Heck carbonylations.

Scheme 9.49 Synthesis of four-membered heterocycles.

Scheme 9.50 Synthesis of five-membered nitrogen heterocycle.

Scheme 9.51 Synthesis of five-membered oxygen heterocycle.

Scheme 9.52 Synthesis of six-membered nitrogen heterocycle.

Scheme 9.53 Synthesis of six-membered Oxa or Thia heterocycle.

Scheme 9.54 Synthesis of larger heterocycle.

Scheme 9.55 Application in synthesis of active drug molecules or natural pro...

Scheme 9.56 Application in industrial production.

Figure 9.1 Frequently used ligands for carbonylation of aryl chlorides.

Figure 9.2 Organic dyes commonly used in photocatalysis [30].

Figure 9.3 Formic acid and its derivatives used as CO source [35].

Figure 9.4 Common nucleophilic reagents used in carbonylations.

Chapter 10

Scheme 10.1 Molecular orbitals of CO.

Scheme 10.2 Carbonylation of Csp

3

compounds.

Scheme 10.3 Carbonylation of allylpalladium species.

Scheme 10.4 Stoichiometric carbonylation of allylpalladium species.

Scheme 10.5 CO inserts into the allylpalladium species.

Scheme 10.6 Two different CO insertion mechanism.

Scheme 10.7 Carbonylation of allylmercury species.

Scheme 10.8 Carbonylation of tributylallylstannane species.

Scheme 10.9 Carbonylation of allylnickel species.

Scheme 10.10 Carbonylation of allyl chlorides to acyl chlorides.

Scheme 10.11 Carbonylation of allyl chlorides to amides.

Scheme 10.12 Carbonylation of allyl chlorides to ketones.

Scheme 10.13 Carbonylation of allyl esters to β, γ-unsaturated esters.

Scheme 10.14 Alkoxycarbonylation of γ-trimethylsilylallyl acetate.

Scheme 10.15 Dicarbonylation of 1, 4-diacetoxy-but-2-ene.

Scheme 10.16 Carbonylation of allyl esters with organozinc compounds.

Scheme 10.17 Carbonylation of allyl esters with aryl boronic acids.

Scheme 10.18 Carbonylation of allyl carbonates.

Scheme 10.19 Decarboxylation-carbonylation of 3-vinyl-1- oxo-2,6-dioxacycloh...

Scheme 10.20 Carbonylation of (Z)-2-en-4-yn carbonates.

Scheme 10.21 Carbonylation of allyl phosphates utilizing different nucleophi...

Scheme 10.22 Asymmetric alkoxycarbonylation of allyl phosphates.

Scheme 10.23 Carbonylation of allyl phosphates with imines to

β

-lactams...

Scheme 10.24 Carbonylation of allyl phosphates with thiazines to bicyclic

β

...

Scheme 10.25 Carbonylation of allyl ethers.

Scheme 10.26 Ni-catalyzed carbonylation of allyl alcohols.

Scheme 10.27 Pd-catalyzed carbonylation of allyl alcohols with aliphatic alc...

Scheme 10.28 Pd-catalyzed carbonylation of allyl alcohols with phenols.

Scheme 10.29 Possible mechanism of Pd-catalyzed carbonylation of allyl alcoh...

Scheme 10.30 Carbonylation of allyl alcohols to thioesters.

Scheme 10.31 Carbonylation of allyl alcohols to acids.

Scheme 10.32 Carbonylation of allyl alcohols to amides.

Scheme 10.33 Carbonylation of allyl amines to amides.

Scheme 10.34 Carbonylation of allyl amines to lactams.

Scheme 10.35 Carbonylation of benzyl bromides to lactones.

Scheme 10.36 Carbonylation of benzyl chlorides with salicylic aldehydes.

Scheme 10.37 Carbonylation of benzyl bromides with metal alkoxides or ethers...

Scheme 10.38 Carbonylation of benzyl halides with epoxides.

Scheme 10.39 Pd-catalyzed carbonylation of benzyl halides to acids.

Scheme 10.40 Co-catalyzed carbonylation of benzyl halides to acids.

Scheme 10.41 Ni-catalyzed carbonylation of benzyl halides to acids.

Scheme 10.42 Carbonylation of benzyl halides to amides.

Scheme 10.43 Carbonylation of benzyl halides with imines to

β

-lactams....

Scheme 10.44 Carbonylation of benzyl halides with heterocycles.

Scheme 10.45 Carbonylation of benzyl halides to ketones.

Scheme 10.46 Carbonylation of benzyl halides with alkynes.

Scheme 10.47 Carbonylation of benzyl halides with aryl iodides.

Scheme 10.48 Carbonylation of benzyl halides with alkyl iodides.

Scheme 10.49 Carbonylation of benzyl alcohols.

Scheme 10.50 Proposed mechanism of alkoxycarbonylation of benzyl alcohols.

Scheme 10.51 Carbonylation of benzyl alcohols to acids.

Scheme 10.52 Carbonylation of benzyl alcohols under basic conditions.

Scheme 10.53 Carbonylation of benzyl quaternary ammonium salt.

Scheme 10.54 Carbonylation of benzyl amines to amides.

Scheme 10.55 Carbonylation of benzyl amines to esters.

Scheme 10.56 Alkoxycarbonylation of benzyl C—H bonds.

Scheme 10.57 Alkoxycarbonylation of mercaptans.

Scheme 10.58 Carbonylation of diazo compounds.

Scheme 10.59 Carbonylation of α-halide carbonyl derivatives.

Scheme 10.60 Alkoxycarbonylation/allylation domino reactions of haloketone....

Scheme 10.61 Carbonylative arylation of potassium malonate monoesters.

Scheme 10.62 Carbonylation of ethyl diazoacetate.

Scheme 10.63 Carbonylation of alkylmercury compounds.

Scheme 10.64 Carbonylation of alkylzinc compounds.

Scheme 10.65 Carbonylation of organoindium compounds.

Scheme 10.66 Carbonylation of alkyl bromides with B(OR)

3

.

Scheme 10.67 Carbonylation of perfluoroalkyl iodides with alkenes.

Scheme 10.68 Carbonylation of perfluoroalkyl iodides with different nucleoph...

Scheme 10.69 Carbonylation of alkyl iodides.

Scheme 10.70 Carbonylation of alkyl bromides with alcohols.

Scheme 10.71 Photocatalytic carbonylation of alkyl halides.

Scheme 10.72 Carbonylation of alkyl sulfonates.

Scheme 10.73 Carbonylation of alkyl bromides with Na

2

Fe(CO)

4

.

Scheme 10.74 Mn-catalyzed carbonylation of alkyl iodides.

Scheme 10.75 Mn-catalyzed carbonylation of alkyl iodides with amides.

Scheme 10.76 Ni-catalyzed reductive carbonylation of alkyl bromides.

Scheme 10.77 Ni-catalyzed reductive carbonylation of alkyl iodides.

Scheme 10.78 Ni-catalyzed reductive carbonylation of benzyl bromides and org...

Scheme 10.79 Rh-catalyzed carbonylation of alkyl halides with phenols.

Scheme 10.80 Carbonylation of cyclic ethers.

Scheme 10.81 Carbonylation of epoxides.

Scheme 10.82 Carbonylation of cyclic ethers with secondary N-silylamines....

Scheme 10.83 Regioselective methoxycarbonylation of chiral epoxides.

Scheme 10.84 Ring-expansion carbonylation of N-heterocycles.

Scheme 10.85 Ring-expansion carbonylation of epoxides.

Scheme 10.86 Ring-expansion carbonylation of lactones.

Scheme 10.87 Ring-expansion carbonylation of epoxides to succinic anhydrides...

Scheme 10.88 Ring-expansion carbonylation of alkenyl-substituted epoxides....

Scheme 10.89 Ring-expansion carbonylation of substituted homoglycidols.

Scheme 10.90 Ring-expansion carbonylation of epoxides with double bonds.

Scheme 10.91 Ring-expansion carbonylation of S-containing heterocycle.

Scheme 10.92 Ring-expanding carbonylation of 2-aryl-2-oxazolines.

Scheme 10.93 Carbonylation of cyclohexane.

Scheme 10.94 Cu-catalyzed carbonylation of alkanes.

Scheme 10.95 Pd-catalyzed alkoxycarbonylation of alkanes.

Scheme 10.96 Metal-free carbonylation of alkanes.

Scheme 10.97 Oxidative double carbonylation of alkanes with amines.

Scheme 10.98 Photocatalytic carbonylation of alkanes.

Scheme 10.99 Pd-catalyzed directing Csp

3

—H bond carbonylation.

Scheme 10.100 Ru-catalyzed directing Csp

3

—H bond carbonylation.

Scheme 10.101 Pd-catalyzed directing Csp

3

—H bond carbonylation of simple ami...

Scheme 10.102 Selective directing Csp

3

—H bond carbonylation of amines.

Chapter 11

Figure 11.1 The Gattermann–Koch reaction.

Figure 11.2 High pressure formylation of isopropyl benzene.

Figure 11.3 Superacid-mediated Gattermann–Koch reactions. (a) With HF–SbF

5

; ...

Figure 11.4 Alternative electrophiles for arene carbonylation. (a) With brom...

Figure 11.5 Scope and limits of the Gattermann–Koch reaction. (a) With subst...

Figure 11.6 Alkane carbonylation with AlCl

3

and proposed mechanism. (a) Mixt...

Figure 11.7 Early examples of superacid catalyzed alkane carbonylation. (a) ...

Figure 11.8 Temperature controlled selectivity for superacid catalyzed carbo...

Figure 11.9 Selectivity and variation of nucleophiles in the acid catalyzed ...

Figure 11.10 SbF

5

-HSO

3

CF

3

mediated adamantane formylation.

Figure 11.11 GaCl

3

-mediated formylation of adamantane.

Figure 11.12 Cobalt catalyzed cyclocarbonylation of imines.

Figure 11.13 Ruthenium catalyzed, chelation assisted α-carbonylation of pyri...

Figure 11.14 Pyridine directed,

o

-carbonylation of arenes.

Figure 11.15 Intermolecular coupling of 2-aryl-heterocycles with alcohols....

Figure 11.16 Carbonylative functionalization of C(sp

3

)—H bonds with a pyridi...

Figure 11.17 Fluorenone synthesis via intramolecular carbonylative C–H funct...

Figure 11.18 Ru(II) catalyzed carbonylative coupling of aryl iodides with he...

Figure 11.19 Amine-directed generation of benzolactams via carbonylative C–H...

Figure 11.20 Rhodium and manganese catalyzed cyclocarbonylations with nitrog...

Figure 11.21 Intramolecular, carbonylative C–H functionalization with

N

-(sp

2

Figure 11.22 Co-catalyzed carbonylative C–H functionalization with a tethere...

Figure 11.23 C(sp

3

)—H bond carbonylation for the synthesis of γ-lactam deriv...

Figure 11.24 Pd-catalyzed carbonylative C–H functionalization to access β-la...

Figure 11.25 Oxygen-directed C—H bond alkoxycarbonylation.

Figure 11.26 Lactones via hydroxy-directed carbonylative C–H functionalizati...

Figure 11.27 Traceless-silanol directing groups for the installation of carb...

Figure 11.28 Photoassisted benzene formylation with IrH

3

(CO)(dppe).

Figure 11.29 Arene formylation with RhCl(CO)(P(CH

3

)

3

)

2

. (a) Benzene carbonyl...

Figure 11.30 Proposed mechanism for RhCl(CO)(P(CH

3

)

3

)

2

catalyzed arene formy...

Figure 11.31 Alkane formylation with RhCl(CO)(P(CH

3

)

3

)

2

.

Figure 11.32 Stoichiometric arene carboxylation with Pd(OAc)

2

.

Figure 11.33 Catalytic arene carboxylation with Pd(OAc)

2

.

Figure 11.34 Aerobic arene carboxylation with Pd(OAc)

2

and co-catalytic HPMo...

Figure 11.35 Rh(III) catalyzed arene carboxylation.

Figure 11.36 Pyridinone ligand-accelerated arene carboxylation.

Figure 11.37 Carbonylative functionalization of heteroarenes to esters.

Figure 11.38 In situ formation of transmetalation active coupling partners f...

Figure 11.39 Ketone synthesis via carbonylative C–H functionalization. (a) I...

Figure 11.40 Ketone synthesis via in situ build up acyl triflate electrophil...

Figure 11.41 Electrophilic Pd/Cu catalyzed alkane carbonylation.

Figure 11.42 RhCl

3

catalyzed synthesis of acetic acid from methane.

Figure 11.43 Radical carbonylation of cyclohexane with di-

t

-butyl peroxide....

Figure 11.44 Carboxylation of alkanes with Fenton's reagent.

Figure 11.45 Copper mediated carboxylation of methane.

Figure 11.46 Vanadium catalyzed alkane carboxylation. (a) VO(acac)

2

catalyst...

Figure 11.47 Metal catalyzed carbonylation of alkanes to imides and esters. ...

Figure 11.48 Photochemical formylation of cyclohexane.

Figure 11.49 Polyoxotungstate photocatalysts for alkane formylation.

Figure 11.50 Alkane formylation with aldehyde photocatalysts.

Chapter 12

Scheme 12.1 Quick guide to a radical carbonylation map.

Scheme 12.2 Selected examples of radical-carbonylation mediated by tin or si...

Scheme 12.3 Selected examples of radical carbonylation under oxidation and r...

Scheme 12.4 Selected examples for atom- and group-transfer carbonylation [8,...

Scheme 12.5 Possible pathways of acyl radicals leading to esters and amides....

Scheme 12.6 Three-component reaction of alkylidenecyclopropanes, CO, and all...

Scheme 12.7 Cyanoborohydride-mediated radical carbonylation.

Scheme 12.8 Hydroxymethylation of alkyl iodides by borohydrides and CO.

Scheme 12.9

N

-heterocyclic-carbene-borane-mediated hydroxymethylation by CO....

Scheme 12.10 (TMS)

3

Si-radical mediated radical carbonylation leading to a sp...

Scheme 12.11 Synthesis of unsymmetrical ketones by C–H carbonylation using T...

Scheme 12.12 Synthesis of amides by C–H carbonylation using TBADT photocatal...

Scheme 12.13 Alkenyl radical carbonylation leading to 1,7-dien-6-one.

Scheme 12.14 Round-trip radical cyclization accompanied by alkenyl radical c...

Scheme 12.15 Tin-mediated radical carbonylation of alkynes leading to α-subs...

Scheme 12.16 Radical-mediated [2+2+1] cycloaddition leading to unsaturated γ...

Scheme 12.17 The first aryl radical carbonylation leading to aldehydes.

Scheme 12.18 Electron-transfer-based aryl radical carbonylation leading to e...

Scheme 12.19 Electron-transfer-based aryl radical carbonylation leading to c...

Scheme 12.20 Electron-transfer-based aryl radical carbonylation leading to a...

Scheme 12.21 Electron-transfer-based aryl radical carbonylation leading to b...

Scheme 12.22 Radical aminocarbonylation of chlorobenzene under UV light irra...

Scheme 12.23 Pd/light catalyzed chlorocarbonylation of aryl halides and in s...

Scheme 12.24 Ir-photocatalyzed aminocarbonylation of aryl halides and alkyl ...

Scheme 12.25 Fluorescein-photocatalyzed alkoxycarbonylation of aryl diazoniu...

Scheme 12.26 Eosin Y-photocatalyzed alkoxycarbonylation of aryl diazonium sa...

Scheme 12.27 Ru-photocatalyzed hydroxycarbonylation of aryl diazonium salts....

Scheme 12.28 Synthesis of diaryl ketone from aryldiazonium salts.

Scheme 12.29 Photocatalyzed carbonylation of aryl sulfonyl chlorides.

Scheme 12.30 Concept of Pd-catalyzed radical carbonylation.

Scheme 12.31 Radical alkoxycarbonylation of alkyl iodides accelerated by Pd ...

Scheme 12.32 Radical double carbonylation via 5-

exo

cyclization accelerated ...

Scheme 12.33 Ligand-directed selective synthesis of α-keto amides and amides...

Scheme 12.34 Carbonylative Sonogashira reaction using alkyl iodides.

Scheme 12.35 Carbonylative Suzuki–Miyaura reaction using alkyl iodides.

Scheme 12.36 Carbonylative Heck reaction using alkyl iodides and arylalkenes...

Scheme 12.37 Four-component coupling involving radical carbonylation.

Scheme 12.38 Pd-catalyzed radical carbonylation under heated conditions.

Scheme 12.39 Pd/light catalyzed chlorocarbonylation of aryl halides and in s...

Scheme 12.40 Cu–NHC complexes catalyzed three-component radical carbonylatio...

Scheme 12.41 Cu–NHC complexes catalyzed radical carbonylation.

Scheme 12.42 Aminocarbonylation of alkyl iodides by Ir-photoredox catalyst....

Scheme 12.43 Carbonylative Heck-type reactions starting from Katritzky salts...

Scheme 12.44 Carbonylative Heck-type reaction via ring-opening catalyzed by ...

Scheme 12.45 Fe-catalyzed carbonylation of tertiary alkyl radicals.

Scheme 12.46 Carbonylative synthesis of β-homoprolines using Cu-catalyst....

Scheme 12.47 Decarboxylative carbonylative alkynylation using Ir-photoredox ...

Scheme 12.48 Carbonylation of alkyl radicals generated from organosilicates ...

Figure 12.1 The occurrence of radical carbonylation in the 1950s and its ren...

Chapter 13

Scheme 13.1 Transition metal catalyzed carbonylation reactions: (a) hydrofor...

Scheme 13.2 Rhodium catalyzed AHF of (a) activated terminal alkenes, (b) 1,1...

Scheme 13.3 Classification of ligands discussed in this chapter for rhodium ...

Scheme 13.4 Hybrid bidentate ligands for rhodium catalyzed AHF of vinyl acet...

Scheme 13.5 Hybrid bidentate ligands for rhodium catalyzed AHF of vinyl acet...

Scheme 13.6 Hybrid bidentate ligands for rhodium catalyzed AHF of vinyl acet...

Scheme 13.7 Non-hybrid bidentate ligands for rhodium catalyzed AHF of vinyl ...

Scheme 13.8 Non-hybrid bidentate ligands for rhodium catalyzed AHF of vinyl ...

Scheme 13.9 Non-hybrid bidentate ligands for rhodium catalyzed AHF of vinyl ...

Scheme 13.10 Non-hybrid bidentate ligands for rhodium catalyzed AHF of vinyl...

Scheme 13.11 Non-hybrid bidentate ligands for rhodium catalyzed AHF of vinyl...

Scheme 13.12 Monodentate ligands for rhodium catalyzed AHF of vinyl acetate,...

Scheme 13.13 Supramolecular ligands for rhodium catalyzed AHF of vinyl aceta...

Scheme 13.14 Supramolecular ligands for rhodium catalyzed AHF of vinyl aceta...

Scheme 13.15 Branch-selective AHF of terminal alkenes with rhodium/bobphos

L

...

Scheme 13.16 Early examples of AHF of 1,2-disubstituted unfunctionalized ole...

Scheme 13.17 Examples of AHF of 1,2-disubstituted functionalized olefins wit...

Scheme 13.18 Reek's supramolecular ligand

L39

for AHF of internal unfunction...

Scheme 13.19 AHF of silyl group-incorporated 1,2-disubstituted olefins.

Scheme 13.20 AHF of heterocyclic olefins with Yanphos

L4-Bn

.

Scheme 13.21 Early examples of AHF of heterocyclic olefins.

Scheme 13.22 AHF of heterocyclic olefins with Reek's hybrid ligand

L41

.

Scheme 13.23 AHF of heterocyclic olefins with Xuphos

L42

.

Scheme 13.24 Examples of linear-selective AHF of 1,1′-disubstituted olefins ...

Scheme 13.25 Examples of branch-selective AHF of 1,1′-disubstituted function...

Scheme 13.26 AHF as the key step in the synthesis of optically pure chiral c...

Scheme 13.27 Attempt in the synthesis of 1

β

-methylcarbapenem using AHF....

Scheme 13.28 Examples of tandem reaction with AHF in the preparation of chir...

Scheme 13.29 Possible coordination modes of rhodium hydride biscarbonyl spec...

Scheme 13.30 General mechanism of rhodium catalyst catalyzed hydroformylatio...

Scheme 13.31 Mechanism of binaphos

L1

In rhodium catalyst catalyzed asymmetr...

Scheme 13.32 Mechanism of bisdiazaphospholane

L21

in rhodium catalyst cataly...

Scheme 13.33 Kinetic model for bisdiazaphospholane

L21

in rhodium catalyst c...

Scheme 13.34 Mechanism of bobphos

L8

in rhodium catalyst catalyzed asymmetri...

Scheme 13.35 Proposed mechanism of bobphos

L4-Bn

in rhodium catalyst c...

Figure 13.1 Model of the transition state in the EDS in AHF with an equatori...

Figure 13.2 AHF reaction in continuous flow using Eli Lily's pipes-in-series...

Chapter 14

Scheme 14.1 Use of diphenylcarbonate (DPC) in the production of polycarbonat...

Scheme 14.2 Some phosgene-free synthetic approaches to DPC: transesterificat...

Scheme 14.3 The first example of catalytic oxidative carbonylation of phenol...

Scheme 14.4 Elementary steps involved in the oxidative carbonylation of phen...

Scheme 14.5 Combined oxidative carbonylation of phenol to DPC and reductive ...

Scheme 14.6 Reoxidation of Pd(0) by benzoquinone (BQ), with formation of Pd(...

Scheme 14.7 Activation of phenol by a Pd

2

–Sn heterotrinuclear complex.

Scheme 14.8 Pd(II)-catalyzed oxidative carbonylation of phenol to DPC perfor...

Scheme 14.9 Formation of monophenylcarbonate-ended BPA oligomers by oxidativ...

Scheme 14.10 Electrochemical reoxidation of Pd(0) to Pd(II) in the carbonyla...

Scheme 14.11 Elementary steps involved in the oxidative carbonylation of phe...

Scheme 14.12 Preparation of a heterogeneous palladium catalyst anchored on s...

Scheme 14.13 Formation of Mn

3

O

4

aerogels through epoxy-driven sol–gel method...

Scheme 14.14 Electrochemical carbonylation of phenol to DPC with a Pd(II) ca...

Scheme 14.15 Electrochemical carbonylation of phenol to DPC with a Pd(0) cat...

Scheme 14.16 Elementary steps involved in the ZnCl

2

-catalyzed conversion of ...

Scheme 14.17 Proposed mechanism for the formation of DPC by (salen)Co(OAc)

2

-...

Scheme 14.18 (a) Base-promoted decarbonylation of methyl formate (MF) follow...

Chapter 15

Scheme 15.1 Synthesis of MDI by oxidative carbonylation process.

Scheme 15.2 Carbamate direct synthesis from diphenylureas.

Scheme 15.3 PdI

2

-catalyzed oxidative carbonylations of amines.

Scheme 15.4 Effect of trace amounts of Fe in oxidative carbonylation.

Scheme 15.5 Ionic liquid-mediated Pd catalyst system for the oxidative carbo...

Scheme 15.6 Synthesis of [Pd-NHC]

2

and aniline–Pd–NHC complex.

Scheme 15.7 Oxidative carbonylation of aniline with methyl formate as carbon...

Scheme 15.8 The structure of [Os

4

Au(

m

-H)

3

(CO)

12

(PPh

3

)].

Scheme 15.9 Trinuclear gold clusters supported by cyclic (alkyl)(amino)carbe...

Scheme 15.10 Synthesis of the [Au

I

]

8

, and bimetallic

clusters.

Scheme 15.11 Synergism of Au and Cu in oxidative carbonylation of amines.

Scheme 15.12 Rh-catalyzed oxidative carbonylation of amines and alcohols.

Scheme 15.13 Cobalt compounds catalyzed oxidative carbonylation of aniline (...

Scheme 15.14 The results of Salen-modified complexes catalyzed oxidative car...

Scheme 15.15 Salen-modified complexes in Li's paper.

Scheme 15.16 Immobilization of Co(salen) in cages of zeolite Y by a “ship in...

Scheme 15.17 Immobilized of Co(salen) by sol–gel method.

Scheme 15.18 Co/N-CNT supported on diatomite prepared by Lu and coworker....

Scheme 15.19 The proposed mechanism of Cu-catalyzed oxidative carbonylation....

Scheme 15.20 Synthesis of NCH–Cu–I catalyst.

Scheme 15.21 Carbonylation of amines with a [(CO)

2

W-(NPh)I

2

]

2

complex.

Scheme 15.22 Sulfur-assisted carbonylation of amines.

Scheme 15.23 Se-catalyzed oxidative carbonylation of piperidine.

Scheme 15.24 Ionic liquids containing anionic selenium species.

Scheme 15.25 Polymer-supported methylselenite.

Scheme 15.26 1,3-Dialkylimidazole-2-selone.

Scheme 15.27 PdCl

2

(MeCN)

2

-catalyzed cross-double carbonylation of amines and...

Scheme 15.28 The possible mechanisms of PdCl

2

(MeCN)

2

-catalyzed cross-double ...

Scheme 15.29 Proposed mechanism for the catalytic carbonylation of a seconda...

Scheme 15.30 The substrate scopes of Pd/C-catalyzed synthesis of oxamates by...

Scheme 15.31 Synthetic steps for the ImmPd-IL@SBA-15 catalyst.

Scheme 15.32 Pd/C-catalyzed oxidative double carbonylation of tertiary amine...

Scheme 15.33 Ethylene glycol from CO by a two-step process.

Scheme 15.34 Oxamate-mediated synthesis of ethylene glycol.

Scheme 15.35 Plausible reaction mechanism of Au-catalyzed double carbonylati...

Scheme 15.36 Oxazolidinones contained commercial antibiotics drugs.

Scheme 15.37 Palladium-catalyzed oxidative carbonylation of β-amino alcohols...

Scheme 15.38 Palladium-catalyzed oxidative carbonylation of β-amino alcohols...

Scheme 15.39 Palladium-catalyzed oxidative carbonylation of β-amino alcohols...

Scheme 15.40 Synthesis of α-oxo carboxylic acids from morpholine-2,3-diones....

Scheme 15.41 Synthesis of 3-(3-(trifluoromethyl)phenyl)octahydropyrido[2,1-

c

Scheme 15.42 The possible mechanism for the double and single carbonylations...

Scheme 15.43 Synthesis of P(DVB-IL)-Pd catalyst.

Scheme 15.44 Electrochemical oxidative carbonylation of amines.

Scheme 15.45 The substrates scope of electrochemical oxidative carbonylation...

Scheme 15.46 Electrochemical oxidative carbonylation of amines with Pd catal...

Chapter 16

Scheme 16.1 4,4′-methylenediphenyldiisocyanate (MDI) and 2,4-toluendiisocyan...

Scheme 16.2 Complexes isolated during mechanistic studies of the palladium/p...

Scheme 16.3 Mechanism of the aniline carbonylation step in the palladium/phe...

Scheme 16.4 Proposal of a palladium imido complex as an intermediate in the ...

Scheme 16.5 Ruthenium imido clusters initially proposed to be intermediates ...

Scheme 16.6 Reaction mechanism for the Ru(CO)

3

(DPPE) catalyzed carbonylation...

Scheme 16.7 Cyclization of

o

-nitrostyrenes to indoles.

Scheme 16.8 Cyclization reactions of different nitroheterocyclic compounds b...

Scheme 16.9 Cyclization of

o

-nitrobiphenyls to carbazoles.

Scheme 16.10 Synthesis of 2

H

-indazoles or benzimidazoles.

Scheme 16.11 Synthesis of quinolones.

Scheme 16.12 Synthesis of dihydroquinoxalines and dihydroquinoxalinones.

Scheme 16.13 Synthesis of β-nitrostyrenes by the Henry reaction.

Scheme 16.14 Synthesis of indoles by cyclization of β-nitrostyrenes.

Scheme 16.15 Synthesis of thienopyrroles by cyclization of β-nitrothiophenes...

Scheme 16.16 Synthesis of pyrroles by cyclization of nitrodienes.

Scheme 16.17 Reaction mechanism for the Ru

3

(CO)

12

/Ar-BIAN catalyzed synthesi...

Scheme 16.18 Synthesis of oxazines and pyrroles by reaction of nitroarenes w...

Scheme 16.19 Synthesis of indoles and

N

-methoxy indoles by reaction of nitro...

Scheme 16.20 Cyclization of

o

-nitrostyrenes to indoles, with formate esters ...

Scheme 16.21 Synthesis of oxazines by reaction of nitroarenes with conjugate...

Scheme 16.22 Cyclization of

o

-nitrobiphenyls to carbazoles, with phenyl form...

Scheme 16.23 Synthesis of quinolones form

o

-nitrochalcones and of indoles fr...

Scheme 16.24 Synthesis of benzimidazolones from

o

-nitroanilines, with TFBen ...

Scheme 16.25 Synthesis of 3,4-dihydroquinazolin-2(1

H

)-ones from

o

-nitrobenzy...

Scheme 16.26 Cyclization of unsaturated nitrothioethers and nitroethers to d...

Scheme 16.27 Ring contraction during the synthesis of 3

H

-indoles from nitros...

Scheme 16.28 Phenyl group migration during the synthesis of 3

H

-indoles from ...

Scheme 16.29 Carbomethoxy group migration during the synthesis of 3

H

-indoles...

Scheme 16.30 Synthesis of indoles from nitrostyrenes, with Mo(CO)

6

as a CO s...

Scheme 16.31 Synthesis of ureas by reaction of nitroarenes and amines, with ...

Scheme 16.32 Synthesis of 2,3-disubstituted quinazolin-4(3

H

)-ones by reactio...

Scheme 16.33 Synthesis of maleimides and α,β-unsaturated amides by reaction ...

Scheme 16.34 Synthesis of unsaturated ketones bearing a pendant amino group ...

Scheme 16.35 Synthesis of indoles and thienopyrroles from β-nitrostyrenes an...

Scheme 16.36 Regioselectivity in the synthesis of ring-fused indoles from β-...

Chapter 17

Figure 17.1 Reaction routes for syngas conversion to ethanol.

Figure 17.2 A proposed mechanism for DME carbonylation on Rh/Cs

2

HPW

12

O

40

....

Figure 17.3 Framework images of MOR (a) and FER (b) viewed along the [001] d...

Figure 17.4 A proposed mechanism of DME carbonylation over zeolites.

Figure 17.5 In situ IR spectra of O–H (a) and C–H (b) regions of DME adsorpt...

Figure 17.6

13

C CP/MAS NMR spectra of the products formed from (a) reaction ...

Figure 17.7 (a) T sites in the MOR framework and (b) schematic illustration ...

Figure 17.8 Reaction pathways for the formation of acetyl from a methyl grou...

Figure 17.9 IR spectra of HMOR (a) and Cu-HMOR (b) upon CO/MeOH co-adsorptio...

Figure 17.10 The correlation of MA yield with Cu

0

(a) and Cu

+

(b) on Cu/...

Figure 17.11 Proposed reaction mechanism for DME carbonylation on the Cu/HMO...

Figure 17.12

ν

(OH)

bands of the H-MOR samples after pyridine desorption...

Figure 17.13 Selective removal of Al atoms in the 12-MR channel of HMOR.

Figure 17.14 Production rate of methyl acetate as a function of the amount o...

Figure 17.15 SEM/TEM images and DME carbonylation performance of micro-sized...

Figure 17.16 DME carbonylation activity and SEM images of HMORs.