Rhodium Catalysis in Organic Synthesis E-Book

Ken Tanaka

• Herausgeber: Wiley-VCH Verlag GmbH & Co. KGaA
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 858

Veröffentlichungsjahr: 2018

Beschreibung

An essential reference to the highly effective reactions applied to modern organic synthesis

Rhodium complexes are one of the most important transition metals for organic synthesis due to their ability to catalyze a variety of useful transformations. Rhodium Catalysis in Organic Synthesis explores the most recent progress and new developments in the field of catalytic cyclization reactions using rhodium(I) complexes and catalytic carbon-hydrogen bond activation reactions using rhodium(II) and rhodium(III) complexes.

Edited by a noted expert in the field with contributions from a panel of leading international scientists, Rhodium Catalysis in Organic Synthesis presents the essential information in one comprehensive volume. Designed to be an accessible resource, the book is arranged by different reaction types. All the chapters provide insight into each transformation and include information on the history, selectivity, scope, mechanism, and application. In addition, the chapters offer a summary and outlook of each transformation. This important resource:

-Offers a comprehensive review of how rhodium complexes catalyze a variety of highly useful reactions for organic synthesis (e.g. coupling reactions, CH-bond functionalization, hydroformylation, cyclization reactions and others)
-Includes information on the most recent developments that contain a range of new, efficient, elegant, reliable and useful reactions
-Presents a volume edited by one of the international leading scientists working in the field today
-Contains the information that can be applied by researchers in academia and also professionals in pharmaceutical, agrochemical and fine chemical companies

Written for academics and synthetic chemists working with organometallics, Rhodium Catalysis in Organic Synthesis contains the most recent information available on the developments and applications in the field of catalytic cyclization reactions using rhodium complexes.

Leseprobe

Table of Contents

Cover

Preface

Part I: Rhodium(I) Catalysis

1 Rhodium(I)‐Catalyzed Asymmetric Hydrogenation

1.1 Introduction

1.2 Chiral Phosphorus Ligands

1.3 Application of Chiral Phosphorus Ligands in Rhodium‐Catalyzed Asymmetric Hydrogenation

1.4 Enantioselection Mechanism of Rhodium‐Catalyzed Asymmetric Hydrogenation

1.5 Conclusion

References

2 Rhodium(I)‐Catalyzed Hydroboration and Diboration

2.1 Introduction

2.2 Hydroboration of Alkenes

2.3 Diboration

2.4 Conclusion

References

3 Rhodium(I)‐Catalyzed Hydroformylation and Hydroamination

3.1 Introduction

3.2 Rhodium(I)‐Catalyzed Hydroformylation

3.3 Rhodium(I)‐Catalyzed Hydroamination

3.4 Conclusion

References

4 Rhodium(I)‐Catalyzed Hydroacylation

4.1 Introduction

4.2 Rhodium(I)‐Catalyzed Intramolecular Hydroacylation

4.3 Rhodium(I)‐Catalyzed Intermolecular Hydroacylation

4.4 Conclusion

References

5 Rhodium(I)‐Catalyzed Asymmetric Addition of Organometallic Reagents to Unsaturated Compounds

5.1 Introduction

5.2 α,β‐Unsaturated Ketones

5.3 α,β‐Unsaturated Aldehydes

5.4 α,β‐Unsaturated Esters

5.5 α,β‐Unsaturated Amides

5.6 α,β‐Unsaturated Phosphonates

5.7 α,β‐Unsaturated Sulfonyl Compounds

5.8 Nitroolefin Compounds

5.9 Alkenylheteroarene and Alkenylarene Compounds

5.10 Conclusion

References

6 Rhodium(I)‐Catalyzed Allylation with Alkynes and Allenes

6.1 Introduction

6.2 Rh(I)‐Catalyzed Addition of O‐Nucleophiles

6.3 Rh(I)‐Catalyzed Addition of S‐Nucleophiles

6.4 Rh(I)‐Catalyzed Addition of N‐Nucleophiles

6.5 Rh(I)‐Catalyzed Addition of C‐Nucleophiles

6.6 Application of Rhodium‐Catalyzed Addition in Total Synthesis

6.7 Conclusion

References

7 Rhodium(I)‐Catalyzed Reductive Carbon–Carbon Bond Formation

7.1 Introduction

7.2 Hydroformylation

7.3 Reductive CC Bond Formation Between Electron‐Deficient Alkenes and Carbonyls or Imines

7.4 Reductive CC Bond Formation Between Less Polarized Carbon‐Based π‐Unsaturated Systems and Carbonyls, Imines, or Anhydrides

7.5 Reductive CC Bond Formation Between Carbon‐Based π‐Unsaturated Systems

7.6 Conclusions

References

8 Rhodium(I)‐Catalyzed [2+2+1] and [4+1] Cycloadditions

8.1 Introduction

8.2 [2+2+1] Cycloaddition

8.3 [4+1] Cycloaddition

8.4 Conclusion

References

9 Rhodium(I)‐Catalyzed [2+2+2] and [4+2] Cycloadditions

9.1 Introduction

9.2 [2+2+2] Cycloaddition

9.3 [4+2] Cycloaddition

9.4 Conclusion

References

10 Rhodium(I)‐Catalyzed Cycloadditions Involving Vinylcyclopropanes and Their Derivatives

10.1 Introduction

10.2 VCP Isomerization Catalyzed by Rh(I)

10.3 Cycloaddition Reactions Using VCPs 5C Synthon

10.4 Cycloaddition Reactions Using VCPs 3C Synthon

10.5 Miscellaneous Cycloaddition

10.6 Conclusion

Acknowledgments

References

11 Rhodium(I)‐Catalyzed Reactions via Carbon–Hydrogen Bond Cleavage

11.1 Introduction

11.2 C–H Arylation

11.3 C–H Alkylation

11.4 C–H Alkenylation

11.5 Tandem Reaction Initiated by C–H Activation

11.6 C–H Borylation

11.7 Undirected Dehydrogenative C–H/Si–H Coupling

11.8 Conclusion

References

12 Rhodium(I)‐Catalyzed Reactions via Carbon–Carbon Bond Cleavage

12.1 Introduction

12.2 Reactions of Cyclopropanes and Cyclobutanes

12.3 Reactions via Cleavage of C(Carbonyl)C Bonds

12.4 Reactions via Directing Group‐Assisted CC Bond Cleavage

12.5 Reactions of Alcohols via CC Bond Cleavage

12.6 Reactions via Cleavage of CCN Bond

12.7 Reactions via Decarbonylation of Aldehydes and Carboxylic Acid Derivatives

12.8 Conclusion

References

Part II: Rhodium(II) Catalysis

13 Rhodium(II) Tetracarboxylate‐Catalyzed Enantioselective C–H Functionalization Reactions

13.1 Introduction

13.2 Mechanistic Insights and General Considerations

13.3 Development of Rh

2

(

S

‐DOSP)

4

as a Chiral Catalyst for C–H Functionalization

13.4 Combined C–H Functionalization/Cope Rearrangement

13.5 Phthalimido Amino Acid‐Derived Catalysts for Intramolecular C–H Functionalization

13.6 Development of Triarylcyclopropane Carboxylate Rh(II) Complexes for Catalyst‐Controlled Site‐Selective C–H Functionalization

13.7 Emerging Chiral Dirhodium Catalyst for Enantioselective C–H Functionalization

13.8 New Paradigms in the Logic of Chemical Synthesis

13.9 Conclusion

Acknowledgments

References

14 Rhodium(II)‐Catalyzed Nitrogen‐Atom Transfer for Oxidation of Aliphatic CH Bonds

14.1 Introduction

14.2 Mechanism‐Inspired Development of New Rh

2

(II) Catalysts

14.3 The Development of New Intramolecular Rh

2

(II)‐Catalyzed sp‐CH Bond Amination

14.4 Intermolecular Rh

2

(II)‐Catalyzed sp‐CH Bond Amination Using an Iodine(III) Oxidant to Generate the Nitrene

14.5 Non‐Oxidatively Generated Nitrenes in Intermolecular Rh

2

(II)‐Catalyzed sp‐CH Bond Amination

14.6 Diastereoselective Rh

2

(II)‐Catalyzed sp‐CH Bond Amination Using Chiral, Non‐racemic Nitrogen‐Atom Precursors

14.7 Enantioselective Rh

2

(II)‐Catalyzed sp‐CH Bond Amination

14.8 Conclusion

References

15 Rhodium(II)‐Catalyzed Cyclopropanation

15.1 Introduction

15.2 Intermolecular Cyclopropanation of Alkenes

15.3 Intramolecular Cyclopropanation of Alkenes

15.4 Cyclopropanation of Poorly Nucleophilic π‐Systems: Alkynes, Arenes, and Allenes as Substrates

15.5 Conclusion

References

16 Reactions of α‐Imino Rhodium(II) Carbene Complexes Generated from

N

‐Sulfonyl‐1,2,3‐Triazoles

16.1 Introduction

16.2 Synthesis of

N

‐Sulfonyl‐1,2,3‐Triazoles

16.3 Reactions of Carbon Nucleophiles with α‐Imino Rhodium(II) Carbene Complexes

16.4 Reactions of Oxygen and Sulfur Nucleophiles with α‐Imino Rhodium(II) Carbene Complexes

16.5 Reactions of Nitrogen Nucleophiles with α‐Imino Rhodium(II) Carbene Complexes

16.6 Conclusion

References

17 Rhodium(II)‐Catalyzed 1,3‐ and 1,5‐Dipolar Cycloaddition

17.1 Introduction

17.2 1,3‐Dipolar Cycloadditions of Carbonyl Ylides

17.3 1,3‐Dipolar Cycloadditions of Azomethine Ylides

17.4 1,3‐Dipolar Cycloadditions of Enoldiazo Compounds

17.5 1,5‐Dipolar Cycloadditions of Pyridinium Zwitterions

17.6 Conclusion

References

Part III: Rhodium(III) Catalysis

18 Rhodium(III)‐Catalyzed Annulative Carbon–Hydrogen Bond Functionalization

18.1 Introduction

18.2 Type A Annulation

18.3 Type B Annulation

18.4 Type C Annulation

18.5 Type D Cyclization

18.6 Conclusion

References

19 Rhodium(III)‐Catalyzed Non‐annulative Carbon–Hydrogen Bond Functionalization

19.1 Introduction

19.2 Alkenylation and Arylation

19.3 Alkynylation

19.4 Alkylation

19.5 CN Bond Formation

19.6 Introduction of CO Bond

19.7 Cyanation

19.8 CO Bond Formation

19.9 CX Bond Formation

19.10 Non‐annulative Thiolation of Arenes

19.11 CSe Bond Formation

19.12 Conclusion

References

20 Sterically and Electronically Tuned Cp Ligands for Rhodium(III)‐Catalyzed Carbon–Hydrogen Bond Functionalization

20.1 Introduction

20.2 Quantitative Models for Steric and Electronic Parameterization of Cp Ligands on Rhodium(III)

20.3 Sterically Tuned Cp Ligands

20.4 Electronically Tuned Cp Ligands

20.5 Conclusion

References

21 Chiral Cp Ligands for Rhodium(III)‐Catalyzed Asymmetric Carbon–Hydrogen Bond Functionalization

21.1 Introduction

21.2 Seminal Work

21.3 The Ligands

21.4 Applications

21.5 Conclusion

References

Index

End User License Agreement

List of Tables

Chapter 1

Table 1.1 Asymmetric hydrogenation of methyl (

Z

)‐α‐acetamidocinnamate (MAC).

Table 1.2 Asymmetric hydrogenation of representative β‐dehydroamino acid esters.

Table 1.3 Asymmetric hydrogenation of dimethyl itaconate.

Chapter 9

Table 9.1 [2+2+2] Cycloaddition of terminal alkynes with dialkyl acetylenedicarb...

Table 9.2 [2+2+2] Cycloaddition of arylacetylenes with 1,4‐butynediol derivative...

Table 9.3 Enantioselective synthesis of planar chiral paracyclophanes.

Table 9.4 [2+2+2] Cycloadditions of heteroatom‐linked diynes with monoynes.

Table 9.6 Enantioselective synthesis of axially chiral biaryls.

Table 9.5 [2+2+2] Cycloaddition of allenynes with monoynes.

Table 9.7 Enantioselective synthesis of chiral tribenzothiepins.

Table 9.8 Enantioselective synthesis of chiral 1,4‐tetraphenylenes.

Table 9.9 Enantioselective synthesis of axially chiral benzamides.

Table 9.11 Enantioselective synthesis of helically chiral 1,1′‐bitriphenylenes.

Table 9.10 Enantioselective synthesis of [7]helicene‐like molecules.

Table 9.12 [2+2+2] Cycloaddition of diynes with nitriles.

Table 9.13 Enantioselective synthesis of axially chiral spirobipyridines.

Table 9.14 Enantioselective synthesis of axially chiral 3‐(2‐halophenyl)pyridine...

Table 9.15 [2+2+2] Cycloaddition of diynes with isocyanates.

Table 9.16 Enantioselective synthesis of axially chiral 6‐aryl‐2‐pyridones.

Table 9.17 Regio‐ and enantioselective [2+2+2] cycloaddition of alkenyl isocyana...

Table 9.18 Enantioselective synthesis of piperidine derivatives via [2+2+2] cycl...

Table 9.19 [2+2+2] Cycloaddition of diynes with carbodiimides.

Table 9.20 [2+2+2] Cycloaddition of diynes with carbon dioxide.

Table 9.21 Enantioselective [2+2+2] cycloaddition of diynes with

exo

‐methylene cy...

Table 9.22 Enantioselective [2+2+2] cycloaddition of 1,6‐enynes with alkynes.

Table 9.23 [2+2+2] Cycloaddition of silylacetylenes, acetylenecarboxylates, and ...

Table 9.24 [2+2+2] Cycloaddition of allene–ene–ynes.

Table 9.25 Enantioselective [2+2+2] cycloaddition of 1,6‐enynes with acrylamides...

Table 9.26 Enantioselective [2+2+2] cycloaddition of enynes with enamides and vi...

Table 9.27 Enantioselective [2+2+2] cycloaddition of dienynes.

Table 9.28 Enantioselective [2+2+2] cycloaddition of ene–allenes with allenoates...

Table 9.29 [2+2+2] Cycloaddition of diynes with carbonyl compounds.

Table 9.30 [2+2+2] Cycloaddition of diynes with carbonyl compounds.

Table 9.31 [2+2+2] Cycloaddition of diynes with imines.

Table 9.32 Intramolecular [2+2+2] cycloaddition of alkynes, allenes, and imines.

Table 9.33 Intramolecular [4+2] cycloaddition of alkynes with dienes.

Table 9.34 [4+2] Cycloaddition of 4‐alkynals with isocyanates: parallel kinetic ...

Chapter 12

Table 12.1 Rhodium(I)‐catalyzed cycloisomerization/cycloaddition reactions of cy...

Table 12.2 Rhodium(I)‐catalyzed transformations of biphenylenes.

Table 12.3 Rhodium(I)‐catalyzed insertion reactions of unsaturated compounds int...

Chapter 14

Table 14.1 Comparison of properties of resorcinol‐derived rhodium(II) complexes ...

Table 14.2 Acyclic stereocontrol in Rh

2

(II)‐catalyzed intermolecular CH bond am...

Table 14.3 Acyclic stereocontrol in Rh

2

(II)‐catalyzed intermolecular CH bond am...

List of Illustrations

Chapter 1

Figure 1.1 Electron‐rich P‐chirogenic phosphine ligands.

Figure 1.2

C

2

symmetric bisphosphacycle ligands possessing

tert

‐buty...

Figure 1.3 P‐Chirogenic three‐hindered quadrant ligands.

Figure 1.4 P‐Chirogenic ligands bearing two or three aryl groups at the ...

Figure 1.5 DuPhos, BPE, and analogous ligands.

Figure 1.6 Ferrocene‐based chiral phosphine ligands.

Figure 1.7

C

2

symmetric bisphosphine ligands with axial chirality.

Figure 1.8 Chiral phosphine–phosphite and phosphine–phosphoramide ligand...

Figure 1.9 Chiral bidentate aminophosphine and phosphinite ligands.

Figure 1.10 Chiral monodentate phosphorus ligands.

Scheme 1.1

Scheme 1.2

Scheme 1.3

Scheme 1.4

Scheme 1.5

Scheme 1.6

Scheme 1.7

Scheme 1.8

Scheme 1.9

Scheme 1.10

Scheme 1.11

Scheme 1.12Scheme 1.12

Scheme 1.13Scheme 1.13

Scheme 1.14Scheme 1.14

Scheme 1.15

Scheme 1.16

Scheme 1.17

Scheme 1.18

Scheme 1.19

Scheme 1.20

Scheme 1.21

Scheme 1.22

Scheme 1.23

Scheme 1.24

Scheme 1.25

Scheme 1.26

Scheme 1.27

Scheme 1.28

Scheme 1.29

Scheme 1.30Scheme 1.30

Scheme 1.31

Scheme 1.32

Scheme 1.33

Scheme 1.34

Scheme 1.35

Scheme 1.36

Scheme 1.37

Scheme 1.38

Scheme 1.39

Scheme 1.40

Scheme 1.41 Reaction of [Rh((

R

)‐TCFP)] – MAC diastereomer complexes with...

Chapter 3

Scheme 3.1 Asymmetric hydroformylation of α‐alkyl acrylates.

Scheme 3.2 Asymmetric hydroformylation of internal olefins using a supra...

Scheme 3.3 Asymmetric hydroformylation of

N

‐allylic anilines using a sca...

Scheme 3.4 Asymmetric hydroformylation of styrenes using formaldehyde.

Scheme 3.5 Asymmetric hydroformylation of internal olefins using parafor...

Scheme 3.6 Transfer hydroformylation between strained olefins and aldehy...

Scheme 3.7 Asymmetric intramolecular hydroamination of olefins.

Scheme 3.8 Asymmetric intermolecular hydroamination of allenes with anil...

Scheme 3.9 Asymmetric intermolecular hydroamination of 1,3‐dienes.

Scheme 3.10 Asymmetric intermolecular hydroamination of alkynes.

Scheme 3.11 Intramolecular anti‐Markovnikov hydroamination of olefins.

Scheme 3.12 Intermolecular anti‐Markovnikov hydroamination of alkenes.

Scheme 3.13 Intermolecular anti‐Markovnikov hydroamination of alkynes.

Scheme 3.14 Proposed mechanism of the anti‐Markovnikov hydroamination of...

Scheme 3.15 Intermolecular anti‐Markovnikov hydroamination of dienes.

Scheme 3.16 Proposed mechanism of the anti‐Markovnikov hydroamination of...

Chapter 4

Scheme 4.1

Scheme 4.2

Scheme 4.3

Scheme 4.4

Scheme 4.5

Scheme 4.6

Scheme 4.7

Scheme 4.8

Scheme 4.9

Scheme 4.10

Scheme 4.11

Scheme 4.12

Scheme 4.13

Scheme 4.14

Scheme 4.15

Scheme 4.16

Scheme 4.17

Scheme 4.18

Scheme 4.19

Scheme 4.20

Scheme 4.21

Chapter 5

Figure 5.1 Chiral phosphorus ligands.

Figure 5.2 Chiral diene ligands.

Figure 5.3 Chiral bis‐sulfoxide ligands and chiral hybrid ligands.

Figure 5.4 Chiral sulfoxide and sulfinamide hybrid ligands.

Scheme 5.1 Ligand‐dependent regioselective (1,2 versus 1,4) addition to ...

Scheme 5.2 Enantioselective addition reaction to α,β‐unsaturated aldehyd...

Scheme 5.3 Enantioselective addition reaction to α,β‐unsaturated esters....

Scheme 5.4 Enantioselective addition reaction to β‐ or γ‐N‐substituted α...

Scheme 5.5 Enantioselective addition reaction to di‐

tert

‐butyl fumarate ...

Scheme 5.6 Diastereoselective addition reaction to α,β‐unsaturated ester...

Scheme 5.7 Enantioselective addition reaction to cyclic α,β‐unsaturated ...

Scheme 5.8 Enantioselective addition reaction to cyclic α,β‐unsaturated ...

Scheme 5.9 Enantioselective addition reaction to maleimides.

Scheme 5.10 Enantioselective addition reaction to α,β‐unsaturated phosph...

Scheme 5.11 Enantioselective addition reaction to α,β‐unsaturated sulfon...

Scheme 5.12 Enantioselective addition reaction to cyclic nitroolefin com...

Scheme 5.13 Enantioselective addition reaction to acyclic nitroolefin co...

Scheme 5.14 Enantioselective addition reaction to alkenylheteroarene and...

Chapter 6

Scheme 6.1 (a) Tsuji–Trost allylation and allylic oxidation. (b) Pd‐cata...

Scheme 6.2 Rh‐catalyzed hydro‐oxycarbonylation of terminal alkynes.

Scheme 6.3 Racemic macrolactonization by applying Breit's methodology.

Scheme 6.4 Plausible mechanism for the Rh‐catalyzed addition of carboxyl...

Scheme 6.5 Asymmetric hydro‐oxycarbonylation of terminal allenes.

Scheme 6.6 First asymmetric rhodium‐catalyzed macrolactonization of ω‐al...

Scheme 6.7 Asymmetric hydro‐oxycarbonylation of terminal alkynes.

Scheme 6.8 Formation of chiral branched allylic ethers by addition of fr...

Scheme 6.9 Formation of chiral branched allylic ethers by addition of fr...

Scheme 6.10 Regioselective hydrosulfination of terminal alkynes and alle...

Scheme 6.11 Asymmetric hydrothiolation of terminal allenes.

Scheme 6.12 Highly

Z

‐selective hydrothiolation of 1,3‐disubstituted alle...

Scheme 6.13 Proposed mechanism for the

Z

‐selective hydrothiolation of 1,...

Scheme 6.14 Nitrogen‐based pronucleophilic addition to terminal allenes ...

Scheme 6.15 Regio‐ and enantioselective hydroamination of terminal allen...

Scheme 6.16 Regiodivergent and enantioselective catalytic addition of 4‐...

Scheme 6.17 Regio‐ and enantioselective rhodium‐catalyzed addition of py...

Scheme 6.18 Regiodivergent and enantioselective catalytic addition of pu...

Scheme 6.19 CC bond formation via Rh‐catalyzed addition of β‐ketoacids,...

Figure 6.1 Application of the Breit‐type rhodium catalysis in total syn...

Chapter 7

Scheme 7.1 Fischer–Tropsch process for the synthesis of alkanes (a) and ...

Scheme 7.2

o

‐DPPB directed hydroformylation of allylic alcohols [8].

Scheme 7.3 Desymmetrization of bisalkenylcarbinol esters using a chiral ...

Scheme 7.4 Alkene hydroformylation using a reversibly bound directing gr...

Scheme 7.5 Chiral scaffolding approach to Rh‐catalyzed alkene hydroformy...

Scheme 7.6 Generalized catalytic cycle for Rh‐catalyzed reductive aldol ...

Scheme 7.7 Morken's asymmetric reductive aldol using Et

2

MeSiH as reducta...

Scheme 7.8 Krische's intramolecular hydrogen‐mediated reductive aldol re...

Scheme 7.9 Krische's intermolecular hydrogen‐mediated reductive aldol re...

Scheme 7.10 Hydrogen‐mediated reductive aldol reactions using a TADDOL‐l...

Scheme 7.11 Krische's hydrogen‐mediated aldol reaction applied to the sy...

Scheme 7.12 Nishiyama's Rh(Phebox)‐catalyzed reductive aldol reaction [3...

Scheme 7.13 Willis' hydroacylative reductive aldol process [41].

Scheme 7.14 Matsuda's reductive Mannich reaction leading to β‐amino este...

Scheme 7.15 Ando and Omote's reductive Mannich coupling to form β‐lactam...

Scheme 7.16 Catalytic generation of vinyl metal species versus stoichiom...

Scheme 7.17 Krische's reductive coupling of dienes and glyoxals [52].

Scheme 7.18 Reductive CC bond formation between alkenes and anhydrides ...

Scheme 7.19 Reductive coupling of 2‐vinyl pyridines with aldimines [55]....

Scheme 7.20 Regio‐ and stereoselective reductive coupling of α‐keto alde...

Scheme 7.21 Two potential mechanistic pathways of the reductive coupling...

Scheme 7.22 Hydrogenative cyclizations of acetylenic aldehydes by Krisch...

Scheme 7.23 Reductive coupling of acetylene and aldimines by Krische and...

Scheme 7.24 Hydrogenative dienylation in the construction of the C(1)–C(...

Scheme 7.25 Reductive coupling of acetylene and aldimines by Krische and...

Scheme 7.26 Krische's C‐propargylation of alcohols with propargyl chlori...

Scheme 7.28 Selective hydro‐ or carbonylative silylcarbocyclizations bet...

Scheme 7.27 Hydrosilylative carbocyclizations reported by Ojima et al. [...

Scheme 7.29 Asymmetric hydrosilylative cyclization of 1,6‐enynes by Wide...

Scheme 7.30 Hydrosilylative carbonylative (2+2+2+1) cycloaddition of end...

Scheme 7.31 Rh‐catalyzed asymmetric cyclization/hydroboration of 1,6‐eny...

Scheme 7.32 Reductive cyclization of 1,6‐enynes by Krische and Jang (a a...

Scheme 7.33 Asymmetric hydrogen‐mediated reductive cyclization of 1,6‐en...

Scheme 7.34 Carbonylative hydrosilylation of 1,5‐diynes by Shibata et al...

Scheme 7.35 Hydrogenative cyclization of 1,6‐diynes by Krische and Yang ...

Chapter 8

Scheme 8.1

Scheme 8.2

Scheme 8.3

Scheme 8.4

Scheme 8.5

Figure 8.1

Scheme 8.6

Scheme 8.7

Scheme 8.8

Scheme 8.9

Scheme 8.10

Scheme 8.11

Scheme 8.12

Scheme 8.14

Scheme 8.13

Scheme 8.15

Scheme 8.16

Scheme 8.17

Scheme 8.18

Scheme 8.19

Scheme 8.20

Scheme 8.21

Scheme 8.22

Scheme 8.23

Scheme 8.24

Scheme 8.25

Scheme 8.26

Scheme 8.28

Scheme 8.27

Scheme 8.29

Scheme 8.30

Scheme 8.31

Scheme 8.32

Scheme 8.34

Scheme 8.33

Scheme 8.35

Scheme 8.36

Scheme 8.37

Scheme 8.38

Chapter 9

Scheme 9.1

Scheme 9.2

Scheme 9.3

Scheme 9.4

Scheme 9.6

Scheme 9.5

Scheme 9.7

Scheme 9.8

Scheme 9.9

Scheme 9.10

Scheme 9.15

Scheme 9.16

Scheme 9.17

Scheme 9.18

Scheme 9.11

Scheme 9.19

Scheme 9.12

Scheme 9.13

Scheme 9.20

Scheme 9.21

Scheme 9.22

Scheme 9.23

Scheme 9.14

Scheme 9.24

Scheme 9.25

Scheme 9.26

Scheme 9.27

Scheme 9.28

Scheme 9.29

Chapter 10

Scheme 10.1

Scheme 10.2

Scheme 10.3

Scheme 10.4

Scheme 10.5

Scheme 10.6

Scheme 10.7

Scheme 10.8

Scheme 10.9

Scheme 10.10

Scheme 10.11

Scheme 10.12

Scheme 10.13

Scheme 10.14

Scheme 10.15

Scheme 10.16

Scheme 10.17

Scheme 10.18

Scheme 10.19

Scheme 10.20

Scheme 10.21

Scheme 10.22

Scheme 10.23

Scheme 10.24

Scheme 10.25

Scheme 10.26

Scheme 10.27

Scheme 10.28

Scheme 10.29

Scheme 10.30

Scheme 10.31

Scheme 10.32

Scheme 10.33

Scheme 10.34

Scheme 10.35

Scheme 10.36

Scheme 10.37

Scheme 10.38

Scheme 10.39

Scheme 10.40

Scheme 10.41

Scheme 10.42

Scheme 10.43

Scheme 10.44

Scheme 10.45

Chapter 11

Scheme 11.1 Intramolecular C–H alkylation initiated by allylic sp

3

CH b...

Scheme 11.2 Direct C–H alkylation of pyridines using α, β‐unsaturated ca...

Scheme 11.3 Branched selective C–H alkylation of azoles using α, β‐unsat...

Scheme 11.4 C–H alkenylation of ketones by the aid of 7‐azaindoline.

Scheme 11.5 Cyclization of diynes initiated by sp

2

CH bond cleavage of ...

Scheme 11.6 Pyridine synthesis initiated by sp

2

CH bond cleavage of α, ...

Scheme 11.7 Cyclic amine synthesis initiated by sp

2

CH bond cleavage of...

Scheme 11.8 Intramolecular cyclization initiated by sp

2

CH bond cleavag...

Scheme 11.9 sp

3

C–H borylation using a Rh catalyst with a silica‐support...

Scheme 11.10 Rh‐catalyzed intermolecular dehydrogenative C–H/Si–H coupli...

Scheme 11.11 C–H silylation for the synthesis of unsymmetric benzosilole...

Scheme 11.12 Enantioselective intramolecular C–H/Si–H coupling for the c...

Scheme 11.13 Intramolecular dehydrogenative sp

3

C–H/Si–H coupling.

Scheme 11.14 C–H silylation along enantioselective intramolecular C–H/Si...

Scheme 11.15 Site‐selective intramolecular C–H/Si–H coupling.

Chapter 12

Scheme 12.1

Scheme 12.2

Scheme 12.3

Scheme 12.4

Scheme 12.5

Scheme 12.6

Scheme 12.7

Scheme 12.8

Scheme 12.9

Scheme 12.10

Scheme 12.11

Scheme 12.12

Scheme 12.13

Scheme 12.14

Scheme 12.15

Scheme 12.16

Scheme 12.17

Scheme 12.18

Scheme 12.19

Scheme 12.20

Scheme 12.21

Scheme 12.22

Scheme 12.23

Scheme 12.24

Scheme 12.25

Scheme 12.26

Scheme 12.27

Scheme 12.28

Scheme 12.30

Scheme 12.31

Scheme 12.29

Scheme 12.32

Scheme 12.33

Scheme 12.34

Scheme 12.35

Scheme 12.36

Scheme 12.37

Scheme 12.38

Scheme 12.39

Scheme 12.40

Scheme 12.41

Scheme 12.42

Scheme 12.43

Scheme 12.44

Scheme 12.45

Scheme 12.46

Scheme 12.47

Scheme 12.48

Scheme 12.49

Scheme 12.50

Scheme 12.51

Scheme 12.52

Scheme 12.53

Scheme 12.55

Scheme 12.54

Scheme 12.56

Scheme 12.57

Scheme 12.58

Scheme 12.59

Scheme 12.60

Scheme 12.61

Scheme 12.62

Scheme 12.63

Scheme 12.64

Scheme 12.65

Scheme 12.66

Scheme 12.67

Scheme 12.68

Scheme 12.69

Scheme 12.70

Scheme 12.71

Scheme 12.72

Scheme 12.73

Scheme 12.74

Scheme 12.75

Scheme 12.76

Scheme 12.77

Scheme 12.78

Scheme 12.79

Scheme 12.80

Scheme 12.81

Chapter 13

Figure 13.1 Catalyst‐controlled site‐selective, diastereoselective, and...

Figure 13.2 General mechanism for dirhodium(II)‐catalyzed C–H insertion ...

Figure 13.3 (a) Most extensively utilized classes of diazo compounds. (b...

Figure 13.4 Electronic activation of various CH bonds versus their ster...

Figure 13.5 Relative rates of C–H functionalization with donor–acceptor ...

Figure 13.6 C–H functionalization reactions are synthetic equivalents to...

Figure 13.7 Introduction to the CHCR transformation.

Figure 13.8 Overview of the CHCR mechanism.

Figure 13.9 Probing the CHCR mechanism using cyclic silylenol ether subs...

Figure 13.10 Diastereocontrol in the CHCR reaction.

Figure 13.11 Surrogate to the vinylogous Mukaiyama aldol reaction.

Figure 13.12 Domino CHCR/elimination reaction sequence for the generatio...

Figure 13.13 Introduction to the phthalimido amino acid‐derived catalyst...

Figure 13.14 Intramolecular C–H functionalization with donor–acceptor ca...

Figure 13.15 Early studies of intramolecular C–H insertion reactions by ...

Figure 13.16 Intramolecular enantioselective C–H insertion into ethylene...

Figure 13.17 Dirhodium(II)‐catalyzed enantioselective C–H functionalizat...

Figure 13.18 Enantioselective C–H insertion into 1,4‐cyclohexadiene with...

Figure 13.19 Trapping α‐diazoimine intermediates with chiral rhodium(II)...

Figure 13.20 Allylic C–H functionalization applied to the synthesis of p...

Figure 13.21 Introduction to the Rh

2

(

S

‐TPCP))

4

catalysts. (a) Synthesis ...

Figure 13.22 Rh

2

(

S

‐

p

‐BrTPCP))

4

‐catalyzed CHCR reaction.

Figure 13.23 Selective C–H functionalization of the primary CH bond of ...

Figure 13.24 Catalyst‐controlled selective C–H functionalization of 2‐me...

Figure 13.25 C–H functionalization of cholesteryl acetate.

Figure 13.26 Site‐, diastereo‐, and enantioselective C–H functionalizati...

Figure 13.27 Site‐selective reactions at primary CH bonds.

Figure 13.28 Axially chiral dirhodium catalysts.

Figure 13.29 Total synthesis of (−)‐incarviatone A.

Figure 13.30 Total synthesis of (−)‐maoecrystal V.

Figure 13.31 Total synthesis of

E

‐δ‐viniferin.

Figure 13.32 Total synthesis of carbon framework of indoxamycin.

Figure 13.33 Total synthesis of (+)‐erogorgiaene, (−)‐colombiasin A, and...

Chapter 14

Scheme 14.1

Scheme 14.2

Scheme 14.3

Scheme 14.4

Scheme 14.5

Scheme 14.6

Scheme 14.7

Scheme 14.8

Scheme 14.9

Scheme 14.10

Scheme 14.11

Scheme 14.12

Scheme 14.13

Scheme 14.14

Scheme 14.15

Scheme 14.16

Scheme 14.17

Scheme 14.18

Scheme 14.19

Scheme 14.20

Scheme 14.21

Scheme 14.22

Scheme 14.23

Scheme 14.24

Scheme 14.25

Scheme 14.26

Scheme 14.27

Scheme 14.28

Scheme 14.29

Scheme 14.30

Scheme 14.31

Scheme 14.32

Scheme 14.33

Scheme 14.34

Scheme 14.35

Scheme 14.36

Scheme 14.37

Scheme 14.38

Scheme 14.39

Scheme 14.40

Scheme 14.41

Scheme 14.42

Scheme 14.43

Scheme 14.44

Scheme 14.45

Scheme 14.46

Scheme 14.47

Scheme 14.48

Scheme 14.49

Scheme 14.50

Scheme 14.51

Scheme 14.52

Scheme 14.53

Scheme 14.54

Scheme 14.55

Scheme 14.56

Scheme 14.57

Scheme 14.58

Scheme 14.59

Scheme 14.60

Chapter 15

Scheme 15.1 Rhodium(II) catalysts commonly encountered in cyclopropanati...

Scheme 15.2 General mechanism of rhodium(II) catalyzed cyclopropanation....

Figure 15.1 Main types of metal‐carbenes found in rhodium(II) catalyzed...

Scheme 15.3 Stereoelectronic trans‐directing effect at the transition st...

Scheme 15.4 Diastereoselective Rh(II)‐catalyzed cyclopropanation via an ...

Scheme 15.5 Asymmetric cyclopropanation of α‐alkyl substituted diazocarb...

Scheme 15.6 Rh

2

(S‐PTAD)

4

‐catalyzed cyclopropanation via a donor‐acceptor...

Scheme 15.7 Enantioselective cyclopropanation of alkenes with α‐styryl d...

Scheme 15.8 Asymmetric Rh

2

(

S

‐NTTL)

4

‐catalyzed cyclopropanation with α‐EW...

Scheme 15.9 Asymmetric Rh

2

(

S

‐TCPTTL)

4

‐catalyzed cyclopropanation with α‐...

Scheme 15.10 Asymmetric Rh

2

(4

S

‐IBAZ)

4

‐catalyzed cyclopropanation with α‐...

Scheme 15.11 Intramolecular Rh(II)‐catalyzed cyclopropanation via an acc...

Scheme 15.12 Asymmetric Rh(II)‐catalyzed cyclopropenation of alkynes.

Scheme 15.13 Asymmetric Rh(II)‐catalyzed cyclopropanation of allenes.

Chapter 16

Scheme 16.1 Early reports on the reaction of

N

‐sulfonyl‐1,2,3‐triazoles....

Scheme 16.2 Synthesis of

N

‐sulfonyl‐1,2,3‐triazoles.

Scheme 16.3 The reaction of 1,3‐dienes, methylenecyclopropanes, and alle...

Scheme 16.4 The reaction of 2,5‐disubstituted furans.

Scheme 16.5 The reaction of C3‐substituted indoles and nonsubstituted in...

Scheme 16.6 The reaction of

N

,

N

‐diethylaniline, anisole, and benzene.

Scheme 16.7 The synthesis of boron aza‐enolates and their application to...

Scheme 16.8 The reaction of aldehydes, α,β‐unsaturated aldehydes, tertia...

Chapter 17

Scheme 17.1 Rh‐catalyzed generation and cycloaddition of carbonyl ylides...

Scheme 17.2 Formation of carbonyl ylides from α‐alkyl diazoesters at low...

Scheme 17.3 [3+2]‐Cycloaddition of carbonyl ylide to form exo‐selective ...

Scheme 17.4 [3+2]‐Cycloaddition of carbonyl ylide with allene to form br...

Scheme 17.5 Endo‐selective cycloaddition of carbonyl ylide with N‐tosyl ...

Scheme 17.6 Role of co‐catalyst in a three‐component carbonyl ylide cycl...

Scheme 17.7 Intra and intermolecular cycloaddition of N‐methylindole wit...

Scheme 17.8 Rh‐catalyzed enantioselective cycloaddition of carbonyl ylid...

Scheme 17.9 Rh‐catalyzed chemoselective cycloadditions of carbonyl ylide...

Scheme 17.10 Chemoselective cycloadditions of bis‐diazo compounds.

Scheme 17.11 Synthesis of Polygalolides A and B utilizing carbonyl ylide...

Scheme 17.12 Application of carbonyl ylide cycloadditions to construct t...

Scheme 17.13 Synthesis of endo‐ and exo‐bicyclic rings through enantiose...

Scheme 17.14 Synthesis of core skeletons of various natural products emp...

Scheme 17.15 Formation of azomethine ylides from imines and cycloadditio...

Scheme 17.16 Rh‐catalyzed generation of azomethine ylide from tartiary a...

Scheme 17.17 Generation of Rh‐carbenes from enoldiazo precursors and rel...

Scheme 17.18 Enantioselective [3+3]‐cycloaddition of Rh‐carbenes with ni...

Scheme 17.19 Rh‐catalyzed cycloadditions of enoldiazo esters with variou...

Scheme 17.20 Catalyst‐controlled variable cycloadditions of enoldiazo es...

Scheme 17.21 Rh‐catalyzed chemo‐, regio‐ and diastereoselective cycloadd...

Scheme 17.22 Rh‐catalyzed synthesis of 1,5‐pyridinium zwitterions from 1...

Scheme 17.23 Three component [5+2] cycloadditions of in situ generated p...

Scheme 17.24 Rh‐catalyzed [5+3] cycloadditions of pyridinium zwitterions...

Scheme 17.25 Rh‐catalyzed enantioselective synthesis of diazocene throug...

Chapter 18

Scheme 18.1

Scheme 18.2

Scheme 18.3

Scheme 18.4

Scheme 18.5

Scheme 18.7

Scheme 18.6

Scheme 18.8

Scheme 18.9

Scheme 18.10

Scheme 18.11

Scheme 18.12

Scheme 18.13

Scheme 18.14

Scheme 18.15

Scheme 18.16

Scheme 18.17

Scheme 18.18

Scheme 18.19

Scheme 18.20

Scheme 18.21

Scheme 18.22

Scheme 18.23

Scheme 18.24

Scheme 18.25

Scheme 18.26

Scheme 18.27

Scheme 18.28

Scheme 18.29

Scheme 18.30

Scheme 18.31

Scheme 18.32

Scheme 18.33

Scheme 18.34

Scheme 18.35

Scheme 18.36

Scheme 18.37

Scheme 18.38

Scheme 18.39

Scheme 18.40

Scheme 18.41

Scheme 18.42

Scheme 18.43

Scheme 18.44

Scheme 18.45

Scheme 18.46

Scheme 18.47

Scheme 18.48

Scheme 18.49

Scheme 18.50

Scheme 18.51

Scheme 18.52

Scheme 18.53

Scheme 18.54

Scheme 18.55

Scheme 18.56

Scheme 18.57

Scheme 18.58

Scheme 18.59

Scheme 18.60

Scheme 18.61

Chapter 19

Scheme 19.1 Rh(III)‐Catalyzed CH Alkenylations of Aryl Pyrazoles.

Scheme 19.2 Rh(III)‐Catalyzed CH Alkenylation of Various Arenes.

Figure 19.1 Mechanism of Rh(III)‐Catalyzed CH Alkenylation.

Figure 19.2 Examples of Rh(III)‐Catalyzed CH Alkenylation.

Scheme 19.3 Rh(III)‐Catalyzed Vinylic CH Alkenylation.

Scheme 19.4 More Examples of Rh(III)‐Catalyzed Vinylic CH Alkenylation....

Figure 19.3 Rh(III)‐Catalyzed Coupling of Bromoarenes with Styrenes.

Scheme 19.5 Rh(III)‐Catalyzed CH Alkenylation of Substrates Bearing Int...

Scheme 19.6 Rh(III)‐Catalyzed CH Alkenylation Using Alkynes.

Figure 19.4 Mechanism of Rh(III)‐Catalyzed CH Alkenylation from Alkynes...

Figure 19.5 Examples of Rh(III)‐Catalyzed CH Alkenylation from Alkynes....

Scheme 19.7 Rh(III)‐Catalyzed C(sp

3

)H Alkenylation of 8‐Methyl quinolin...

Figure 19.6 Mechanism of Rh(III)‐Catalyzed Coupling of Quinoline

N

‐oxide...

Scheme 19.8 Rh(III)‐Catalyzed Redox‐Neutral Coupling of

N

‐phenoxyacetami...

Scheme 19.9 Rh(III)‐Catalyzed Redox‐Neutral Coupling of Quinoline

N

‐oxid...

Scheme 19.10 Rh(III)‐Catalyzed CDC Reactions with Halogenated Benzenes. ...

Figure 19.7 Mechanism of Rh(III)‐Catalyzed CH Arylation.

Scheme 19.11 Rh(III)‐Catalyzed CDC Reactions with Simple Benzene Derivat...

Scheme 19.12 Rh(III)‐Catalyzed CDC Reactions of Indoles/Pyrroles with He...

Scheme 19.13 Rh(III)‐Catalyzed CDC Reactions of Pyridine Directing Arene...

Scheme 19.14Scheme 19.14 Rh(III)‐Catalyzed CDC Reactions with Thiophenes o...

Scheme 19.15Scheme 19.15 Rh(III)‐Catalyzed CDC Reactions Between Pyridines...

Scheme 19.16Scheme 19.16 Rh(III)‐Catalyzed CDC Reactions Between Carboxyli...

Scheme 19.17Scheme 19.17 Rh(III)‐Catalyzed CDC Reactions Between Oximes an...

Scheme 19.18 Rh(III)‐Catalyzed CDC Reactions Between Azobenzenes and Het...

Scheme 19.19 Rh(III)‐Catalyzed Decarboxylative Ortho‐heteroarylation.

Scheme 19.20 Rh(III)‐Catalyzed CH Arylation with Arylboronic Acids.

Scheme 19.21 Rh(III)‐Catalyzed C(sp

3

)H Arylation with Triarylboroxines....

Figure 19.8 Mechanism of Rh(III)‐catalyzed C(sp

3

)H Arylation.

Scheme 19.22 Rh(III)‐Catalyzed β or γ‐C(sp

3

)H Arylation with Triarylbor...

Scheme 19.23 Rh(III)‐Catalyzed CH Arylation with Arylsilanes.

Scheme 19.24 Rh(III)‐Catalyzed CH Arylation with Iodobenzenes.

Figure 19.9 Mechanism of Rh(III)‐Catalyzed CH Coupling with Iodobenzene...

Figure 19.10 Mechanism of Rh(III)‐Catalyzed CH Coupling with 7‐Oxabenzo...

Scheme 19.25 Rh(III)‐Catalyzed CH Naphthylation Using 7‐Oxabenzonorbony...

Scheme 19.26 Rh(III)‐Catalyzed CH Arylation Using 4‐Hydroxycyclohexa‐2,...

Figure 19.11 Mechanism of Rh(III)‐Catalyzed CH Coupling with 4‐Hydroxyc...

Scheme 19.27 Rh(III)‐Catalyzed CH Arylation Using Quinone Diazides.

Figure 19.12 Mechanism of Rh(III)‐Catalyzed CH Coupling with Quinone Di...

Scheme 19.28 Rh(III)‐Catalyzed CH Arylation of 6

th

Position of 2‐Pyrido...

Scheme 19.29 Rh(III)‐Catalyzed Internal Oxidative CDC Reactions.

Scheme 19.30 Rh(III)‐Catalyzed CH Alkynylation with Silyl‐EBXs.

Figure 19.13 Mechanism of Rh(III)‐Catalyzed CH Alkynylation from Silyl‐...

Figure 19.14 Rh(III)‐catalyzed CH Alkynylation from Silyl‐EBXs.

Scheme 19.31 Rh(III)‐Catalyzed CH Alkylation with Diazo Compounds.

Figure 19.15 Mechanism of Rh(III)‐Catalyzed CH Coupling with Diazo Comp...

Figure 19.16 Examples of Rh(III)‐Catalyzed CH Coupling with Diazo Compo...

Scheme 19.32 Rh(III)‐Catalyzed CH Alkylation between

N

‐phenoxyacetamide...

Scheme 19.33 Rh(III)‐Catalyzed Synthesis of Ortho‐Alkenyl Phenols.

Scheme 19.34 Rh(III)‐Catalyzed C(sp

3

)H Alkylation.

Figure 19.17 Mechanism of Rh(III)‐Catalyzed CH Allylation.

Figure 19.18 Examples of Rh(III)‐Catalyzed CH Allylation.

Scheme 19.35 Rh(III)‐Catalyzed Coupling of Azobenzenes with Allyl Acetat...

Scheme 19.36 Regioselectivity of Rh(III)‐Catalyzed Coupling of Arenes wi...

Scheme 19.37 Rh(III)‐Catalyzed CH Allylation with Allenes.

Scheme 19.38 [Rh(III)Cp*]‐Catalyzed Enantioselective CH Allylation.

Scheme 19.39 Rh(III)‐Catalyzed CH Allylation with 4‐Vinyl‐1,3‐dioxolan‐...

Figure 19.19 Examples of Rh(III)‐Catalyzed CH Coupling with 4‐Vinyl‐1,3...

Scheme 19.40 Rh(III)‐Catalyzed CH Allylation with Vinyl Benzoxazinanone...

Scheme 19.41 Rh(III)‐Catalyzed CH Allylation with 2‐Vinyloxiranes.

Scheme 19.42 Rh(III)‐Catalyzed Synthesis of Propenoic Acids.

Scheme 19.43 Rh(III)‐Catalyzed CH Allylation with Vinylcyclopropanes.

Scheme 19.44 Rh(III)‐Catalyzed CH Allylation with Allyl Bromides.

Scheme 19.45 [Cp

E

RhCl

2

]

2

Catalyzed CH Allylation with Aliphatic Alkenes...

Scheme 19.46 Rh(III)‐Catalyzed Coupling of

N

‐acetylbenzamides with 1,3‐D...

Scheme 19.47 Rh(III)‐Catalyzed CH Alkylation with α,β‐Unsaturated Aceto...

Figure 19.20 Mechanism of Rh(III)‐Catalyzed CH Coupling with α,β‐Unsatu...

Figure 19.21 Examples of Rh(III)‐Catalyzed CH Alkylation from α,β‐Unsat...

Scheme 19.48 Rh(III)‐Catalyzed CH Alkylation with Nitroalkenes.

Scheme 19.49 Rh(III)‐Catalyzed Coupling of C(sp

3

)H bonds of 8‐Methylqui...

Scheme 19.50 Rh(III)‐Catalyzed Coupling of C(sp

3

)H bonds with α,β‐Unsat...

Scheme 19.51 Rh(III)‐Catalyzed Coupling of Arenes or Heteroarenes with A...

Figure 19.22 Mechanism of Rh(III)‐Catalyzed CH Coupling with Allylic Al...

Scheme 19.52 Rh(III)‐Catalyzed Alkylation of C(sp

3

)H bonds with Allylic...

Scheme 19.53 Rh(III)‐Catalyzed Alkylation with Cyclic Alkenyl Carbonates...

Scheme 19.54 Rh(III)‐Catalyzed CH Alkylation with 7‐Oxa‐ or 7‐Azabenzon...

Scheme 19.55 Rh(III)‐Catalyzed CH Alkylation with Aldehydes.

Figure 19.23 Mechanism of Rh(III)‐Catalyzed CH Alkylation to Generate B...

Figure 19.24 Examples of Rh(III)‐Catalyzed CH Alkylation to Generate Be...

Scheme 19.56 Rh(III)‐Catalyzed CH Alkylation with Imines.

Figure 19.25 Mechanism of Rh(III)‐Catalyzed CH Alkylation Using Imines....

Figure 19.26 Examples of Rh(III)‐Catalyzed CH Alkylation Using Imines. ...

Scheme 19.57 Rh(III)‐Catalyzed CH Alkylation with

N

‐perfluorobutanesulf...

Scheme 19.58 Rh(III)‐Catalyzed CH Alkylation with Aziridines.

Figure 19.27 Mechanism of Rh(III)‐Catalyzed CH Alkylation Using Aziridi...

Scheme 19.59 Rh(III)‐Catalyzed CH Alkylation with Cyclopropanols.

Figure 19.28 Mechanism of Rh(III)‐Catalyzed CH Alkylation Using Cyclopr...

Scheme 19.60 Rh(III)‐Catalyzed CH Alkylation with Diazabicycles.

Scheme 19.61 Rh(III)‐Catalyzed CH Alkylation with Potassium Alkyltriflu...

Figure 19.29 Mechanism of Rh(III)‐Catalyzed CH Alkylation Using RBF

3

K. ...

Figure 19.30 Rh(III)‐Catalyzed CH Benzylation and Allylation Using Orga...

Scheme 19.62 Rh(III)‐Catalyzed CH Amination of Oximes Using

N

‐chloroami...

Figure 19.31 Examples of Rh(III)‐Catalyzed CH Amination with

N

‐chloroam...

Scheme 19.63 Rh(III)‐Catalyzed CH Amination Using Aryl Azides.

Scheme 19.64 Rh(III)‐Catalyzed CH Amination Using Benzyl or Alkyl Azide...

Scheme 19.65 Rh(III)‐Catalyzed CH Amination in Aqueous medium.

Scheme 19.66 Rh(III)‐Catalyzed Synthesis of

N

‐arylhydroxylamines.

Scheme 19.67 Rh(III)‐Catalyzed Synthesis of Diarylamines Using nitrosobe...

Figure 19.32 Mechanism of Rh(III)‐Catalyzed CH Amination with Nitrosobe...

Scheme 19.68 Ligand‐Promoted Rh(III)‐Catalyzed CH Amination.

Figure 19.33 Mechanism of Ligand‐Promoted Rh(III)‐Catalyzed Amination.

Scheme 19.69 Rh(III)‐Catalyzed CH Amidation Using Sulfonyl Azides.

Figure 19.34 Mechanism of Rh(III)‐Catalyzed CH Amidation Using TsN

3

.

Figure 19.35 Examples of Rh(III)‐Catalyzed CH Amination Using Azides as...

Scheme 19.70 Rh(III)‐Catalyzed C(sp

3

)H Amidation of 8‐Methylquinolines....

Scheme 19.71 Rh(III)‐Catalyzed CH Amidation Using Various Nitrogen Sour...

Scheme 19.72 Rh(III)‐Catalyzed CH Amidation Using Amidobenziodoxolones....

Scheme 19.73 Rh(III)‐Catalyzed CH Amidation Using

tert

‐Butyl 2,4‐dinitr...

Scheme 19.74 Rh(III)‐Catalyzed CH Amidation Using 1,4,2‐Dioxazol‐5‐ones...

Scheme 19.75 Rh(III)‐Catalyzed C(sp

3

)H Amidation Using 1,4,2‐Dioxazol‐5...

Scheme 19.76 Rh(III)‐Catalyzed CH Amidation Using Anthranils.

Scheme 19.77 Rh(III)‐Catalyzed CH Amidation Using

N

‐hydroxycarbamates. ...

Figure 19.36 Mechanism of Rh(III)‐Catalyzed CH Amidation Using

N

‐hydrox...

Scheme 19.78 Rh(III)‐Catalyzed CH Amidation Using Sulfonamides.

Figure 19.37 Mechanism of Rh(III)‐Catalyzed CH Amidation Using Sulfonam...

Scheme 19.79 Rh(III)‐Catalyzed C(sp

3

)H Amidation Using Sulfonamide.

Figure 19.38 Examples of Rh(III)‐Catalyzed CH Acylation with Aldehydes....

Scheme 19.80 Rh(III)‐Catalyzed CH Acylation Using Diarylcyclopropenones...

Scheme 19.81 Rh(III)‐Catalyzed CH Acylation Using Ketenes.

Scheme 19.82 Rh(III)‐Catalyzed CH Amidation Using Isocyanates.

Figure 19.39 Mechanism of Rh(III)‐Catalyzed CH Cyanation with NCTS.

Figure 19.40 Examples of Rh(III)‐Catalyzed CH Cyanation with NCTS.

Scheme 19.83 Rh(III)‐Catalyzed CH Acetoxylation and Hydroxylation.

Figure 19.41 Mechanism of Rh(III)‐Catalyzed CH Acetoxylation.

Figure 19.42 Examples of Rh(III)‐Catalyzed CH Halogenation.

Figure 19.43 Mechanism of Rh(III)‐Catalyzed CH Bromination with NBS.

Scheme 19.84 Rh(III)‐Catalyzed CH Halogenation.

Figure 19.44 Mechanism of Rh(III)‐Catalyzed CH Bromination with NaBr.

Scheme 19.85 Rh(III)‐Catalyzed CH Hyperiodination.

Figure 19.45 Mechanism of Rh(III)‐Catalyzed CH Hyperiodination.

Scheme 19.86 Rh(III)‐Catalyzed CH Thiolation.

Scheme 19.87 Rh(III)‐Catalyzed CH Thiolation of Phenols and Anilines.

Figure 19.46 Mechanism of Rh(III)‐Catalyzed CH Thiolation.

Scheme 19.88 Rh(III)‐Catalyzed CH Selenylation.

Figure 19.47 Mechanism of Rh(III)‐Catalyzed CH Selenylation.

Chapter 20

Scheme 20.1 Structurally diverse Cp ligands [6–27].

Scheme 20.2 Electronic and steric parameters for Cp

X

‐ligated rhodium(III...

Scheme 20.3 Earlier studies by Satoh, Miura, and coworkers [15].

Scheme 20.4 Synthesis of (dihydro)isoquinolones by Rh(III)‐catalyzed C–H...

Scheme 20.5 Improvement of regioselectivity with the Cp

t

ligand [11, 1...

Scheme 20.6 Plausible rationale of regioselectivity based on X‐ray cryst...

Scheme 20.7 Improvement of regioselectivity of pyridone synthesis when u...

Scheme 20.8 Regiodivergent dihydroisoquinolone synthesis by Cramer and c...

Scheme 20.9 Regiodivergent dihydroisoquinolone synthesis by Cramer and c...

Scheme 20.10 Multivariate model for dihydroisoquinolone regioselectivity...

Scheme 20.11 Cyclopropene annulation with

O

‐pivaloyl benzhydroxamic acid...

Scheme 20.12 Multivariate model for diastereoselectivity. Discovery of t...

Scheme 20.13 Rh(III)‐catalyzed synthesis of pyridines by annulation of α...

Scheme 20.14 Diastereodivergent alkene cyclopropanation with

N

‐enoxyphth...

Scheme 20.15 Stereospecific alkene carboamination with

N

‐enoxyphthalimid...

Scheme 20.16 Rh(III)‐catalyzed synthesis of pyridines by annulation of α...

Scheme 20.17 Rh(III)‐catalyzed synthesis of dihydropyridines. Rate accel...

Scheme 20.18 Fagnou's Rh(III)‐catalyzed indole synthesis. Improvement of...

Scheme 20.19 Isochromene synthesis via C–H/O–H activation with [Cp

E

RhCl

2

Scheme 20.20 Construction of 3,4‐fused indoles using [Cp

E

RhCl

2

]

2

as cata...

Scheme 20.21 Oxidative olefination of anilides with alkenes by Glorius a...

Scheme 20.22 Oxidative C–H bond allylation with aliphatic alkenes by Tan...

Scheme 20.23 Tandem [2+2+2] annulation–lactamization of acetanilides wit...

Scheme 20.24 Transition‐metal‐catalyzed oxidative [4+2] annulations of b...

Scheme 20.25 Decarboxylative and oxidative [2+2+2] annulation of benzoic...

Scheme 20.26 Switch between [4+2] and [4+1] annulation by adjusting the ...

Chapter 21

Scheme 21.1 First examples of Cp

X

Rh(III)‐catalyzed enantioselective CH ...

Scheme 21.2 Design principles behind the development of Cp

X

Rh(III) compl...

Figure 21.1 Summary of known Cp

X

Rh complexes.

Scheme 21.3 General methods for the generation of Cp

X

Rh and Cp

X*

Rh compl...

Scheme 21.4 General mechanism for hydroxamate‐directed Cp

X

Rh(III) method...

Scheme 21.5 Hydroxamate‐directed functionalization with allene coupling ...

Scheme 21.6 Hydroxamate‐directed methodologies with alkene and alkyne co...

Scheme 21.7 Hydroxamate‐directed functionalization with electrophilic co...

Scheme 21.8 Cp

X

Rh‐catalyzed CH functionalization of aryl hydroxamates w...

Scheme 21.9 CH functionalization methodologies directed by substituted ...

Scheme 21.10 Hydroxy‐directed [3+2] spiroannulation methodologies.

Scheme 21.11 Enantioselective synthesis of spirocyclic sultams.

Scheme 21.12 Amide‐directed enantioselective addition to nitroalkenes.

Scheme 21.13 Synthesis of

P

‐chiral phosphinamides.

Guide

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Rhodium Catalysis in Organic Synthesis

Methods and Reactions

Edited byKen Tanaka

Copyright

Editor

Prof. Ken Tanaka

Tokyo Institute of Technology

Department of Applied Chemistry

Ookayama, Meguro‐ku

152‐8550 Tokyo

Japan

Cover Image: © Pobytov/Getty Images

All books published by Wiley‐VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

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Preface

Synthetic organic reactions catalyzed by transition‐metal complexes are widely used as useful methods for constructing complex molecular structures. Among them, rhodium complexes show high catalytic activity and wide applicability for various organic transformations, making it an extremely important transition metal, although rhodium is one of the most expensive transition metals. However, rhodium‐catalyzed organic reactions are diverse, and books that classified and introduced them in a systematic manner have not been published. Under these circumstances, Professor P. Andrew Evans edited Modern Rhodium‐Catalyzed Organic Reactions in 2005. This book organized the rhodium‐catalyzed organic reactions for the first time, and I have always put it on the desk as a bible of the rhodium‐catalyzed organic reactions.

Over more than 10 years have passed since its publication; synthetic organic reactions using rhodium complexes as catalysts have further advanced, and new fields have been developed. In particular, remarkable progress and new field development were seen in catalytic cyclization reactions using rhodium(I) complexes and catalytic carbon–hydrogen bond activation reactions using rhodium(II) and rhodium(III) complexes. Therefore, in this revised edition, I focused on the progress after the former edition and the new fields that were not dealt with in the former edition. Experts in each field have written each chapter and provided important insight into each transformation including the history, selectivity, scope, mechanism, and application. Additionally, the chapters also include a summary and outlook of each transformation. I am convinced that as this book provides an invaluable overview of recent important progress in this important research area, this book will be useful not only for experts in this field but also for researchers who are about to enter in both academic institutions and companies.

I would like to thank the authors of the individual chapters, each of whom is acknowledged as a world expert in their research area of the rhodium‐catalyzed reactions, for their efforts in writing manuscripts. This book project cannot be accomplished without their patience. I would also like to thank the members of my research group for their assistance in the preparation of index and the team at Wiley‐VCH, especially Dr. Elke Maase and Mr. Lesley Jebaraj, for their valuable assistance and encouragement during this book project.

June 2018

Ken Tanaka

Part IRhodium(I) Catalysis

1Rhodium(I)‐Catalyzed Asymmetric Hydrogenation

Tsuneo Imamoto

Chiba University, Faculty of Science, Department of Chemistry, Yayoi‐cho, Inage‐ku, 263‐8522 Chiba, Japan

1.1 Introduction

The asymmetric hydrogenation of prochiral unsaturated compounds, such as alkenes, ketones, and imines, is one of the most straightforward methods for the synthesis of optically active compounds. This method using molecular hydrogen and small amounts of chiral transition‐metal complexes is operationally simple, environmentally friendly, and frequently employed in both academia and industry.

During the last five decades, the homogeneous asymmetric hydrogenation by the use of rhodium, ruthenium, iridium, and other transition‐metal complexes has remarkably progressed with the developments of thousands of chiral ligands. The catalytic performance of asymmetric hydrogenation is largely affected by the used transition metal, and rhodium‐catalyzed hydrogenation has constituted a unique and large research area to provide useful technologies for the production of optically active pharmaceuticals, agrochemicals, and fine chemicals.

Previously, Chi, Tang, and Zhang described an excellent review of Rh‐catalyzed asymmetric hydrogenation covering the literatures published until 2003 [1]. This review describes the subsequent advancement of this area, citing the literatures published since 2004.

1.2 Chiral Phosphorus Ligands

Chiral phosphorus ligands play pivotal roles in Rh‐catalyzed asymmetric hydrogenation as well as in many other transition‐metal‐catalyzed asymmetric transformations [2]. Although numerous chiral phosphorus ligands have been designed and synthesized over the past half a century and many of them have been used in both academia and industry, the work to develop more efficient ligands is still actively underway. This section summarizes the chiral phosphorus ligands used for Rh‐catalyzed asymmetric hydrogenation that have been reported since 2004. They are largely classified into several types according to their structural variations, electronic properties, and characteristic activities toward prochiral unsaturated substrates.

1.2.1 P‐Chirogenic Bisphosphine Ligands

1.2.1.1 Electron‐Rich C2 Symmetric Ligands

BisP*‐ and MiniPHOS‐Based Ligands

BisP* and MiniPHOS are typical P‐chirogenic phosphine ligands, possessing a bulky alkyl group and a methyl group at the phosphorus atoms (Figure 1.1). These ligands exhibit excellent enantioselectivities in some representative catalytic asymmetric reactions, but because of their high air sensitivity, they are not widely used, except in the mechanistic study of Rh‐catalyzed asymmetric hydrogenation [3]. Further studies to overcome the drawbacks of these ligands, QuinoxP* [4, 5], Ad‐QuinoxP* [6], L1[7], AlkynylP* [8], BenzP* [5, 9], DioxyBenzP* [5], TMB‐QuinoxP* [10], and BipheP* [11] have been designed and synthesized (Figure 1.1). Among these ligands, QuinoxP* and BenzP* are air‐stable crystalline solids and are frequently used not only in Rh‐catalyzed asymmetric hydrogenation but also in many other catalytic asymmetric transformations [12].

Figure 1.1Electron‐rich P‐chirogenic phosphine ligands.

Bisphosphacycle Ligands

In 2002, Tang, Zhang, and coworkers reported the synthesis of a P‐chirogenic bisphospholane ligand, TangPhos, and its excellent enantioinduction ability and high catalytic activity in Rh‐catalyzed asymmetric hydrogenation [13, 14]. The superior catalytic performance of the TangPhos‐Rh complex is responsible for its very rigid molecular structure consisting of three fused five‐membered rings and the asymmetric environment arising from the tert‐butyl groups that effectively shield the two diagonal quadrants. The great success of TangPhos ligand has prompted the synthesis of analogous bisphosphacycle ligands, all of which possess tert‐butyl groups at the P‐chirogenic phosphorus atoms (Figure 1.2). A seven‐membered bisphosphacycle ligand, Binapine, exhibits high enantioinduction ability in the hydrogenation of β‐dehydroamino acids and 2‐pyridyl‐substituted ketones [15, 16]. DiSquareP* and L2, which contain highly strained four‐membered phosphacycles, have their potential utility in Rh‐catalyzed asymmetric hydrogenation [17, 18]. In 2005, Liu and Zhang reported DuanPhos ligand composed of two connected benzophospholanes [19]. Both enantiomers of this ligand are commercially available and widely used in Rh‐catalyzed asymmetric hydrogenation of various prochiral substrates and often employed in the industrial production of chiral ingredients [20]. ZhangPhos ligand is more rigid and electron‐rich than TangPhos and DuanPhos, and it shows exceedingly high enantioselectivities in the hydrogenation of not only standard probing substrates but also N‐aryl β‐enamino esters and α‐aryl imino esters [21]. Tang and coworkers have developed P‐chirogenic bisoxaphospholane ligands BIPOP and WingPhos [22, 23]. These ligands provide unique catalytic performance and have been successfully employed in the hydrogenation that difficultly proceeds with the use of other predecessor ligands [24].

Figure 1.2C2 symmetric bisphosphacycle ligands possessing tert‐butyl groups at the P‐chirogenic centers.

1.2.1.2 Three‐Hindered Quadrant Ligands

In 2004, Hoge and coworkers reported a novel C1 symmetric bisphosphine ligand, di‐tert‐butylphosphino‐tert‐butyl(methyl)phosphinomethane named Trichickenfootphos (TCFP) [25]. This ligand forms a four‐membered Rh complex, in which the three tert‐butyl groups effectively hinder three quadrants, and its superior catalytic performance was demonstrated by the highly efficient synthesis of a pregabalin precursor [25a]. The three‐hindered quadrant motif, apart from the traditional C2 symmetric design concept, has prompted the synthesis of analogous ligands (L3[26], MaxPHOS [27], L4[28], MeO‐POP [29], 3H‐BenzP* [30a], 3H‐QuinoxP* [30]) (Figure 1.3). All of these ligands have proved their high catalytic activities in Rh‐catalyzed asymmetric hydrogenations of various substrates.

Figure 1.3P‐Chirogenic three‐hindered quadrant ligands.

1.2.1.3 Ligands Bearing Two or Three Aryl Groups at the Phosphorus Atom

DIPAMP synthesized by Knowles and coworkers is a landmark chiral phosphine ligand in the history of Rh‐catalyzed asymmetric hydrogenation. Nevertheless, the ligand has not been widely used because of its high but somewhat insufficient enantioselectivities (up to 96% in the hydrogenation of α‐dehydroamino acid derivatives) and the inconvenient synthesis with traditional methods. New synthetic methodology using phosphine‐boranes as the intermediates has enabled the synthesis of analogous ligands (L5[31], L6[32], R‐SMS‐Phos [33], L7[34], L8[35]) (Figure 1.4). Among these ligands, L5 and R‐SMS‐Phos provide superior enantioselectivities up to >99% in comparison with DIPAMP. Ligands L7 and L8 exhibit unique catalytic performance, arising from the supramolecular component and the large bite angle of the Rh complex.

Figure 1.4P‐Chirogenic ligands bearing two or three aryl groups at the phosphorus atom.

1.2.2 DuPhos, BPE, and Analogous Ligands

DuPhos and BPE possessing chiral phospholanyl cycles are versatile ligands not only for Rh‐catalyzed asymmetric hydrogenation but also for many other transition‐metal‐catalyzed reactions. The great success of DuPhos and BPE provided the opportunity to synthesize ferrocene‐based ligands, FerroTANE and Ph‐5‐Fc, with the chiral phosphacycle motif. Furthermore, several analogous ligands (UlluPHOS [36], Butiphane [37], PhBPM [38], Ph‐Quinox [39], Ph‐Pyrazine [39], and CatASiumMQF [40]) have been reported since 2004 (Figure 1.5). Among all of these bisphosphacycle ligands, DuPhos is still the most frequently used in Rh‐catalyzed asymmetric hydrogenation.

Figure 1.5DuPhos, BPE, and analogous ligands.

1.2.3 Ferrocene‐Based Bisphosphine Ligands

In 1974, Hayashi and coworkers synthesized a chiral ferrocene‐based bisphosphine ligand, BPPFA, and demonstrated its high catalytic performance in Rh‐catalyzed asymmetric hydrogenation. Since Hayashi's pioneering work, numerous ferrocene‐based chiral phosphorus ligands have been synthesized and applied in catalytic asymmetric reactions. Figure 1.6 shows ferrocene‐based phosphorus ligands, most of which have been reported since 2004.

Figure 1.6Ferrocene‐based chiral phosphine ligands.

A landmark discovery in this area is Josiphos ligand, developed by Togni and coworkers in 1994. The ligand has been widely used not only in Rh‐catalyzed asymmetric hydrogenation but also in many other catalytic asymmetric reactions [41]. Another notable ligand is a trans‐chelating ligand, TRAP, synthesized by Kuwano et al. in 1991. This ligand with its unique coordination style provides characteristic enantioselectivity and activity in various asymmetric transformations and is particularly useful for Rh‐catalyzed hydrogenation of indole derivatives [42]. BoPhoz ligand developed by Boaz is a phosphine–aminophosphine ligand. By selecting the substituents on the phosphorus atoms, the BoPhoz‐Rh catalyst provides excellent enantioselectivity and reactivity in the hydrogenation of various prochiral substrates [43]. TaniaPhos [44], Walphos [45], MandyPhos [44b, 45a] are commercially available as the ligand kits with the substituent variations on the phosphorus atoms. It is possible to control the enantioselectivity and activity by ligand of choice according to prochiral substrates. PingFer [46], TriFer [47], and BoPhoz* [48] possess P‐chirogenic center in addition to the planar chiral ferrocene backbone. ImiFerroPhos [49], ClickFerrophos I [50], ClickFerrophos II [51], L9[52], ZhaoPhos [53], ChenPhos [54], Wudaphos [55], tBu‐Wudaphos [56], and SPO‐Wudaphos [57] have been synthesized recently and proved their characteristic enantioinduction abilities and employed in the asymmetric hydrogenations that had long been difficultly achieved. For example, ZhaoPhos exhibits high enantioselectivities in the hydrogenation of nitroalkenes, substituted quinolines and isoquinolines, and imines, by means of the hydrogen bonding interaction of the thiourea component with the substrate functional groups. ChenPhos, Wudaphos, tBu‐Wudaphos, and SPO‐Wudaphos, all of which contain a dimethylamino group in the ligand molecules, promote the hydrogenation of the substrates bearing acidic functionalities via non‐covalent ion pair interaction.

1.2.4 C2 Symmetric Triaryl‐ or Diarylphosphine Ligands with Axial Chirality

The ligands of this class, particularly BINAP and SEGPHOS, are frequently used as benchmark ligands in Ru‐catalyzed asymmetric hydrogenation and many other catalytic asymmetric reactions [58]. New ligands, such as o‐Ph‐MeO‐BIPHEP [59], Me‐CATAPHOS [60], and SKP [61], have been added in this class since 2004 (Figure 1.7), and each ligand has shown characteristic activity in Rh‐catalyzed asymmetric hydrogenation. For example, SKP‐Rh complex bearing a large bite angle is effective for the hydrogenation of β‐branched enol esters and can be used for the synthesis of optically active primary alcohols with excellent enantiomeric excesses (ee's) [61b].

Figure 1.7C2 symmetric bisphosphine ligands with axial chirality.

1.2.5 Phosphine–Phosphite and Phosphine–Phosphoramide Ligands

Phosphine–phosphite and phosphine–phosphoramide ligands are often used in Rh‐catalyzed asymmetric hydrogenation [62]. As shown in Figure 1.8, new ligands, such as o‐BINAPHOS [63], L10[64], Me‐AnilaPhos [65], PEAPhos [66], L11[67], THNAPhos [68], L12[69], L13[70], L14[71], HY‐Phos [68b], L15[72], L16[72], Quinaphos [73], L17[74], and L18[75], have been added in this class. Most of these ligands possess rigid chiral backbones such as binaphthyl, biphenyl, and TADDOL moieties and provide high to excellent enantioselectivities in the Rh‐catalyzed hydrogenation of α‐ and β‐dehydroamino acid derivatives, enamides, and enol esters.

Figure 1.8Chiral phosphine–phosphite and phosphine–phosphoramide ligands.

Figure 1.9Chiral bidentate aminophosphine and phosphinite ligands.

1.2.6 Other Bidentate Ligands

Figure 1.9 shows other bidentate phosphorus ligands bearing two aryl substituents on the phosphorus atoms. Bisaminophosphine ligands, L19[76] and L20[77], exhibit high enantioselectivities of up to 99.9% in the hydrogenation of α‐dehydroamino acid derivatives and dimethyl itaconate. A phosphine–aminophosphine ligand, L21[43e], has been successfully utilized for the hydrogenation of α,β‐unsaturated phosphonates with benzoyloxy or acylamino group at the α‐position. A bisphosphinite ligand, SpiroBIP [78], is less reactive and of somewhat lower enantioinduction ability in the hydrogenation of standard α‐dehydroamino acid derivatives in comparison with the bisaminophosphine ligands L19 and L20.

Figure 1.10Chiral monodentate phosphorus ligands.

1.2.7 Monodentate Phosphorus Ligands

Monodentate phosphorus ligands are also useful for Rh‐catalyzed asymmetric hydrogenation. Typically, the MonoPhos family with wide substituent diversity is often used for the ligand optimization in Rh‐catalyzed asymmetric hydrogenation by utilizing high‐throughput screening methods [79]. In addition to MonoPhos, SIPHOS [80], L22[81], DpenPhos [82], FAPhos [83], PhthalaPhos [84], L23[82b], and L24[85] have been reported since 2004 (Figure 1.10