Carbon Monoxide in Organic Synthesis E-Book
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- Herausgeber: Wiley-VCH GmbH
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- Sprache: Englisch
Carbon Monoxide in Organic Synthesis
A thoroughly up-to-date overview of carbonylation reactions in the presence of carbon monoxide
In Carbon Monoxide in Organic Synthesis: Carbonylation Chemistry, expert researcher and chemist Bartolo Gabriele delivers a robust summary of the most central advances in the field of carbonylation reactions in the presence of carbon monoxide. Beginning with a brief introduction on the importance of carbon monoxide as a building block in modern organic synthesis, the author goes on to describe metal-catalyzed carbonylations utilizing iron, cobalt, nickel, copper, and manganese.
Descriptions of palladium, ruthenium, and rhodium-catalyzed reactions follow, as do discussions of metal-free carbonylation processes.
The book is organized by metal to make the book useful as a guide for researchers from both academia and industry whose work touches on the direct synthesis of carbonyl compounds, carboxylic acid derivatives, and heterocycles. It aims to stimulate further discoveries in this rapidly developing field.
Readers will also enjoy:
- A thorough introduction to carbonylations promoted by first row transition metal catalysts, including cobalt-catalyzed and nickel-catalyzed carbonylations
- An exploration of carbonylations promoted by second row transition metal catalysts, including ruthenium-, rhodium-, palladium(0)-, and palladium (II)-catalyzed carbonylations
- Practical discussions of miscellaneous carbonylation reactions, including carbonylations promoted by third row transition metal catalysts and metal-free carbonylation processes
Perfect for catalytic and organic chemists, Carbon Monoxide in Organic Synthesis: Carbonylation Chemistry is also an indispensable resource for chemists working with organometallics and industrial chemists seeking a summary of important processes used to synthesize value-added products.
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Seitenzahl: 668
Veröffentlichungsjahr: 2021
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Table of Contents
Cover
Title Page
Copyright
Dedication
Preface
1 Introduction: Carbon Monoxide as Synthon in Organic Synthesis
References
Part I: Carbonylations Promoted by First Row Transition Metal Catalysts
2 Cobalt‐Catalyzed Carbonylations
2.1 Introduction
2.2 Carbon Monoxide and Its Surrogates
2.3 Hydroformylation of Alkenes
2.4 Carbonylation of Alkynes by the Pauson–Khand [2+2+1] Reaction
2.5 Carbonylation of Methanol
2.6 Carbonylation of Heterocycles
2.7 Carbonylation of Alkyl and Aryl Halides
2.8 CH Bond Carbonylations
2.9 Miscellaneous Co‐Catalyzed Carbonylations
2.10 Summary and Conclusions
References
3 Nickel‐Catalyzed Carbonylations
3.1 Introduction
3.2 Nickel Halides in Carbonylation Reaction
3.3 Ni‐Chelates as Precatalysts
3.4 Nanoparticles as Active Catalysts
3.5 Dinickel Complexes as Catalysts
3.6 Ni/AC as a Promising Heterogeneous Catalyst
3.7 Use of CO Surrogates with Nickel Catalysts
3.8 Other Prominent Roles of Nickel in Carbonylation
3.9 Conclusion and Future Outlook
References
4 Carbonylations Catalyzed by Other First Row Transition‐Metal Catalysts (Manganese, Iron, Copper)
4.1 Introduction
4.2 Synthesis of Ketones
4.3 Synthesis of Esters
4.4 Synthesis of Amides
4.5 Synthesis of Other Products
4.6 Summary and Conclusions
References
Part II: Carbonylations Promoted by Second Row Transition Metal Catalysts
5 Ruthenium‐Catalyzed Carbonylations
5.1 Introduction
5.2 CH Activation of Nitrogen‐Containing Arene Derivatives
5.3 Ruthenium‐Catalyzed Carbonylations of Olefins and Nitroarenes
5.4 Ruthenium‐Catalyzed Carbonylation of Amines and Alcohols
5.5 Ruthenium‐Catalyzed Cyclocarbonylations
5.6 Ruthenium‐Catalyzed Reactions Using Syngas
5.7 Synthesis of Oxo Products from H2 and CO2
5.8 Conclusions
References
6 Rhodium‐Catalyzed Carbonylations
6.1 Introduction
6.2 Hydroformylation
6.3 Carbonylation
6.4 Some Relevant Patents and Patent Applications (2015–2020)
6.5 Summary and Conclusions
References
7 Palladium(0)‐Catalyzed Carbonylations
7.1 Introduction
7.2 Palladium(0)‐Catalyzed Carbonylative Synthesis of Ester Derivatives
7.3 Palladium(0)‐Catalyzed Carbonylative Synthesis of Amide Derivatives
7.4 Palladium(0)‐Catalyzed Carbonylative Synthesis of Ketone Derivatives
7.5 Palladium(0)‐Catalyzed Carbonylative Synthesis of α,β‐Alkynyl Ketones Derivatives
7.6 Palladium(0)‐Catalyzed Carbonylative Synthesis of Other Carbonyl Compounds
7.7 Summary and Conclusions
References
8 Palladium(II)‐Catalyzed Carbonylations
8.1 Introduction
8.2 Palladium(II)‐Catalyzed Carbonylation of Alkanes and Saturated CH Bonds
8.3 Palladium(II)‐Catalyzed Carbonylation of Arenes and Heteroarenes
8.4 Palladium(II)‐Catalyzed Carbonylation of Alkenes
8.5 Palladium(II)‐Catalyzed Carbonylation of Alkynes
8.6 Palladium(II)‐Catalyzed Carbonylation of Other Substrates
8.7 Summary and Conclusions
References
9 Carbonylations Catalyzed by Other Second‐Row Transition Metal Catalysts
9.1 Introduction
9.2 Zirconium Compounds as Carbonylation Catalysts
9.3 Silver Compounds in Carbonylation Reactions
9.4 Molybdenum Compounds in Carbonylation Reactions
9.5 Summary and Conclusions
References
Part III: Miscellaneous Carbonylation Reactions
10 Carbonylations Promoted by Third‐Row Transition Metal Catalysts
10.1 Introduction
10.2 Methanol Carbonylation
10.3 Hydroformylation
10.4 Other Carbonylation Reactions
10.5 Summary and Conclusions
References
11 Transition Metal‐Free Carbonylation Processes
11.1 Introduction
11.2 Transition‐Metal‐Free Carbonylation for the Synthesis of Aldehydes and Ketones
11.3 Transition‐Metal‐Free Carbonylation for the Synthesis of Esters and Lactones
11.4 Transition‐Metal‐Free Carbonylation for the Synthesis of Amides
11.5 Transition‐Metal‐Free Carbonylation for the Synthesis of Acids and Anhydrides
11.6 Transition‐Metal‐Free Carbonylation for the Synthesis of Acyl Chlorides and Alcohols
11.7 Summary and Conclusions
References
12 Conclusions and Perspectives
Index
End User License Agreement
List of Tables
Chapter 3
Table 3.1 Methanol carbonylation with different loading of catalysts.
Chapter 9
Table 9.1 SZ‐catalyzed Koch reaction.
Table 9.2 Carbonylation reactions in the presence of the Ag(I)/H
2
SO
4
system....
Table 9.3 Reductive carbonylation of nitrobenzene
a)
.
Table 9.4 Intramolecular Mo‐carbonylative addition to haloaryl‐ and haloalke...
Table 9.5 Palladium‐catalyzed Mo(CO)
6
‐promoted carbonylation of aryl iodides...
List of Illustrations
Chapter 1
Scheme 1.1 Reactions of carbon monoxide with free radicals, carbocations, or...
Scheme 1.2 Carbon monoxide coordinated to a metal center becomes more suscep...
Scheme 1.3 An acyl‐ or aroyl‐metal intermediate (R = carbon group) undergoin...
Scheme 1.4 An example of catalytic carbonylation process in which the metal ...
Scheme 1.5 An example of catalytic carbonylation process in which the metal ...
Scheme 1.6 Possible mechanistic pathways in the nucleophilic displacement st...
Scheme 1.7 A generic direct carbonylation process (a) and direct carbonylati...
Scheme 1.8 A generic substitutive carbonylation process (a) and substitutive...
Scheme 1.9 A generic additive carbonylation process for an olefin (a), addit...
Scheme 1.10 A generic oxidative carbonylation process (a) with the eliminati...
Scheme 1.11 PdI
2
‐catalyzed oxidative dialkoxycarbonylation of alkynes to mal...
Scheme 1.12 (a) A generic reductive carbonylation process with molecular hyd...
Chapter 2
Scheme 2.1 General hydroformylation transformation of a terminal alkene yiel...
Chart 2.1 Sterically hindered phosphabicyclononane ligands.
Scheme 2.2 Simplified mechanism of the cobalt‐mediated hydroformylation of a...
Figure 2.1 η
2
‐acyl structure of the unsaturated [Co(COR)(CO)
2
(PR′
3
)] species...
Scheme 2.3 Key steps of the H
2
activation in the hydrogenolysis of the acyl ...
Scheme 2.4 Tris(
p
‐sulfonatophenyl)phosphine (TPPTS) ligand and α‐cyclodextri...
Scheme 2.5 Selective hydroformylation reaction of epoxy‐alkenes
7
.
Scheme 2.6 Hydroformylation of propylene oxide
8
.
Scheme 2.7 Proposed mechanism for the hydroformylation of
8
.
Scheme 2.8 Synthesis of cyclopentenones via [2+2+1] cycloaddition of an alky...
Scheme 2.9 Simplified catalytic cycle of the Pauson–Khand reaction.
Scheme 2.10 Effects of the tether length on the intramolecular Pauson–Khand ...
Scheme 2.11 Intramolecular diastereo‐ and enantioselective Pauson–Khand annu...
Scheme 2.12 QuinoxP* and ThaxPhos alkyne complexes.
Scheme 2.13 Synthesis of a key intermediate of
19
via an intermolecular Paus...
Scheme 2.14 Catalytic Pauson–Khand reaction in the absence of external CO, p...
Scheme 2.15 Applications of the Pauson–Khand reaction in the elaboration of ...
Scheme 2.16 Carbonylation of epoxides catalyzed by [Co(CO)
4
]
−
and assi...
Scheme 2.17 Main steps of epoxides carbonylation reactions catalyzed by [LA]
Scheme 2.18 Regioselective carbonylation of 1,2‐disubstituted epoxides.
Scheme 2.19 Double carbonylation reaction of racemic epoxide
29
into
31
.
Scheme 2.20 Regiodivergent carbonylation of
cis
‐1,2‐disubstituted epoxides
3
...
Scheme 2.21 Late‐stage carbonylation reaction in the total synthesis of (−)‐...
Scheme 2.22 Carbonylation of aziridines catalyzed by [Co(CO)
4
]
−
assist...
Scheme 2.23 Synthesis of pyrrolidinones
43
and
44
from azetidine and CO.
Scheme 2.24 Cobalt‐catalyzed carbonylation of 2‐phenylthiirane in the presen...
Scheme 2.25 Alternating copolymerization of propylene oxide and CO catalyzed...
Scheme 2.26 Copolymerization of azetidine and CO in 1,4‐dioxane or THF.
Scheme 2.27 Cobalt‐catalyzed carbonylation reaction of oxazolidines
47
in the...
Scheme 2.28 Carbonylation of alky‐ and aryl‐substituted oxazolines under hyd...
Scheme 2.29 Synthesis of
51
under hydroformylation reaction conditions.
Scheme 2.30 Synthesis of phenyl and phenyl‐substituted acetic acids under ph...
Scheme 2.31 Monocarbonylation of aryl halides into the corresponding aryl me...
Scheme 2.32 Cobalt‐catalyzed carbonylation of Schiff base
55
.
Scheme 2.33 Cobalt‐catalyzed C–H carbonylation of benzamides
57
.
Scheme 2.34 Proposed catalytic cycle for the oxidative N–H and C–H activatio...
Chart 2.2 General substrate scope of the CO annulation reaction with differe...
Scheme 2.35 Cobalt‐catalyzed cyclization of CO, isocyanates
67
, and epoxides...
Scheme 2.36 Cobalt‐catalyzed cyclization of CO, imine
70
, and epoxide
8
.
Scheme 2.37 Cobalt‐catalyzed copolymerization of imines and CO into polypept...
Chapter 3
Scheme 3.1 Amide synthesis.
Scheme 3.2 Plausible reaction mechanism of amide formation.
Scheme 3.3 Synthetic protocol of difluoroalkyl ketones. Source: Modified fro...
Scheme 3.4 Radical mechanism pathway for the synthesis of difluoroalkyl keto...
Scheme 3.5 Undesired processes in Ni‐catalyzed carbonylative coupling of sec...
Figure 3.1 Pharmaceutical drugs obtained by Ni‐catalyzed carbonylative coupl...
Scheme 3.6 Amide synthesis (
acac
,
acetylacetonate
; DTBP, di‐
tert
‐butylperoxi...
Scheme 3.7 Mechanism of amide synthesis.
Scheme 3.8 Schematic representation of synthesis of isoindolinones.
Scheme 3.9 The role of nickel catalyst as a Lewis acid and for CH bond func...
Scheme 3.10 Carbonylative cross‐coupling in the presence of Ni(COD)
2
catalys...
Scheme 3.11 Ni(COD)
2
/PCy
3
‐catalyzed carbonylative cycloaddition of the 1,5‐e...
Scheme 3.12 [2+2+1] Carbonylative asymmetric cycloaddition.
Scheme 3.13 Mechanism of [2+2+1] carbonylative cycloaddition.
Scheme 3.14 Suzuki carbonylation by
in situ
generated nanocatalyst.
Scheme 3.15 Catalytic carbonylation of acetylene.
Scheme 3.16 Stoichiometric Pauson–Khand and norbornadiene carbonylation reac...
Scheme 3.17 Ethanol carbonylation.
Scheme 3.18 Vapor‐phase carbonylation of methanol.
Scheme 3.19 Cross‐electrophile coupling by Ni catalyst (
dtbbpy
, 4,4′‐
di‐tert
...
Scheme 3.20 Thiocarbonylation reaction and general mechanism of alkoxy, amin...
Figure 3.2 NiCl
2
(dmg) catalyst (
dmg
,
dimethylgloxime
).
Scheme 3.21 Ni(OTf)
2
‐mediated carbonylation.
Scheme 3.22 Mechanism for the carbonylation of aryl iodides with indole deri...
Scheme 3.23 Synthesis of alkyl iodides with cyclic ether THF.
Scheme 3.24 Use of formate as CO source for carbonylation.
Scheme 3.25 NiBr
2
·diglyme‐catalyzed carbonylation to obtain dialkyl ketones ...
Scheme 3.26 Ligand‐free pathway for carbonylative Sonogashira reaction (
dppb
Scheme 3.27 1,2‐Iminoacylation of oxime ester‐tethered alkenes.
Scheme 3.28 Pincer ligands used for carbonylative Negishi coupling. CO gas w...
Scheme 3.29 Ni‐pincer‐mediated carbonylation of benzyl bromide.
Scheme 3.30 Mechanism of carbonylative Negishi coupling.
Scheme 3.31 Carbonylation of α‐bromonitriles and alkyl zinc reagents in the ...
Scheme 3.32 Synthesis of β‐ketonitriles.
Scheme 3.33 Proposed mechanism of formation cyclopentanone derivatives.
Scheme 3.34 Ni/Fe
3
O
4
‐catalyzed indirect carbonylation.
Scheme 3.35 Indirect carbonylative cycloaddition of unactivated amides (here...
Scheme 3.36 Microwave‐assisted indirect carbonylation of arylboronic acids t...
Scheme 3.37 Carbonylative Suzuki reaction. Diaryl is obtained only at 5 bar ...
Scheme 3.38 Carbonylative polymerization of THF and EO. Here, THF also act a...
Scheme 3.39 Synthetic scope of flavones using the carbonylative Sonogashira...
Chapter 4
Scheme 4.1 CuI‐catalyzed carbonylative cross‐coupling of organostannanes and...
Scheme 4.2 NanoCu‐catalyzed carbonylative Suzuki coupling of aryl iodides wi...
Scheme 4.3 Cu/Mn bimetallic catalysis of carbonylative Suzuki–Miyaura reacti...
Figure 4.1 Copper/manganese bimetallic‐catalyzed mechanism for the carbonyla...
Scheme 4.4 IPrCuCl‐catalyzed hydrocarbonylative CC coupling of terminal alk...
Scheme 4.5 Cu(TMHD)
2
‐catalyzed carbonylative Sonogashira coupling reaction o...
Scheme 4.6 Iron‐catalyzed carbonylative Suzuki reactions.
Scheme 4.7 Fe(OTf)
2
‐catalyzed carbonylative alkyl‐acylation of heteroarenes....
Scheme 4.8 (NHC)Cu(I)/Pd(II)‐catalyzed four‐component borocarbonylation of v...
Figure 4.2 Proposed mechanism for the Cu/Pd‐catalyzed borocarbonylation of v...
Scheme 4.9 IPrCuCl‐catalyzed borocarbonylation of unactivated alkenes with a...
Figure 4.3 Proposed mechanism for the IPrCuCl‐catalyzed borocarbonylation of...
Scheme 4.10 CuTc/Fe
3
(CO)
12
‐catalyzed alkoxycarbonylation of unactivated alky...
Scheme 4.11 Cu(I)‐catalyzed carbonylation of alkanes with alcohol and amine ...
Scheme 4.12 CuBr(Me
2
S)‐catalyzed carbonylative four‐component reaction of et...
Scheme 4.13 Mn
2
(CO)
10
‐catalyzed carboacylation of alkenes with alkyl iodides...
Scheme 4.14 Fe(acac)
3
‐catalyzed carbonylative cyclization of γ,δ‐unsaturated...
Scheme 4.15 Mn(OAc)
3
·H
2
O‐catalyzed ring‐opening carbonylation of aryl cyclob...
Figure 4.4 Plausible mechanism for the Mn‐catalyzed ring‐opening carbonylati...
Scheme 4.16 Cu(OTf)
2
‐catalyzed carbonylation of
N
‐fluoro‐sulfonamides to syn...
Scheme 4.17 Cu or Mn‐catalyzed carbonylative coupling of alkyl iodides with ...
Figure 4.5 Plausible mechanism for the Cu‐catalyzed carbonylative coupling o...
Scheme 4.18 IPrCuI/NHC‐catalyzed double carbonylation reaction.
Scheme 4.19 Fe
3
(CO)
12
‐catalyzed carbonylation for the synthesis of succinimi...
Scheme 4.20 Microwave‐assisted aminocarbonylation of ynamides.
Scheme 4.21 [Fe
3
CO
12
]‐catalyzed carbonylation of terminal alkynes.
Figure 4.6 Plausible mechanism for the iron‐catalyzed carbonylation of alkyn...
Scheme 4.22 MnBr(CO)
5
‐catalyzed C–H aminocarbonylation of heteroarenes.
Figure 4.7 Proposed mechanism for the manganese(I)‐catalyzed C–H aminocarbon...
Scheme 4.23 Cu(OAc)
2
‐catalyzed carbonylation of C(sp
2
)H bonds with MeNO
2
....
Scheme 4.24 Cu
2
O‐catalyzed aminocarbonylation of arylboronic acids with
N
‐ch...
Scheme 4.25 Cu(OTf)
2
‐catalyzed intermolecular aminocarbonylation of remote C...
Scheme 4.26 CuF
2
‐catalyzed carbonylative acetylation of amines.
Scheme 4.27 K
2
[Fe(CO)
4
]‐catalyzed carbonylation of tertiary amines.
Figure 4.8 Proposed mechanism for the [Fe(CO)
4
]‐catalyzed carbonylation of t...
Scheme 4.28 Fe(acac)
3
‐catalyzed intramolecular aminocarbonylation of oxime e...
Scheme 4.29 Synergistic copper‐catalyzed reductive aminocarbonylation of nit...
Scheme 4.30 Synthesis of allylic alcohols via
Cl
IPrCuCl‐catalyzed hydrocarbo...
Scheme 4.31 (NHC)CuCl‐catalyzed borocarbonylative coupling of internal alkyn...
Figure 4.9 Proposed mechanism for the borocarbonylative coupling of alkynes ...
Scheme 4.32
Me
IPrCuCl‐catalyzed carbonylative hydroxymethylation of unactiva...
Figure 4.10 Proposed mechanism for the
Me
IPrCuCl‐catalyzed carbonylative hyd...
Scheme 4.33 IPrCuCl‐catalyzed carbonylative silylation of alkyl halides.
Scheme 4.34 IPr·CuCl‐catalyzed synthesis of stereodefined cyclopropyl bis(bo...
Figure 4.11 Derivatization of the BC bond of cyclopropyl bis(boronates) (PM...
Figure 4.12 Plausible reaction mechanism for the IPr·CuCl‐catalyzed synthesi...
Scheme 4.35 CuBr(Me
2
S)‐catalyzed carbonylation of indoles with hexaketocyclo...
Scheme 4.36 CuCl
2
·2H
2
O‐promoted double carbonylation.
Scheme 4.37 Cu(OAc)
2
‐catalyzed carbonylation to synthesize carbamates.
Scheme 4.38 CuI
2
‐catalyzed carbonylation reaction to synthesize oxime carbon...
Chapter 5
Scheme 5.1 The reaction mechanism for the acylation of pyridine.
Scheme 5.2 Acylation of 1,2‐dimethylimidazole.
Scheme 5.3 (a) Acylation occurs only on the 2‐position of imidazole. (b) Acy...
Scheme 5.4 (a) Electron‐rich 1‐methyl‐2‐phenylimidazole is mainly acylated a...
Scheme 5.5 (a) Acylation can occur on each
ortho
position of the phenyl...
Scheme 5.6 Hydroaroylation of styrene using water as solvent.
Scheme 5.7 Removing the directing group under ring closure to indenones.
Scheme 5.8 The protecting and deprotecting concept for the 2‐phenyloxazoline...
Scheme 5.9 Carbonylative Suzuki coupling of
N
,
N
‐dimethyl‐2‐pyridinylaniline....
Scheme 5.10 (a) Rh
4
(CO)
12
activates the sp
3
‐hybridized carbon atoms of piper...
Scheme 5.11 (a) Ru
3
(CO)
12
activates the sp
3
‐hybridized CH bond of the
tert
‐b...
Scheme 5.12 Hydroformylation of 10‐undecenitrile.
Scheme 5.13 Cp*RuH/Xantphos‐catalyzed hydroformylation of 1‐decene.
Scheme 5.14 One catalyst system (Ru
3
(CO)
12
/
L1
) can give either (a) linear al...
Scheme 5.15 Hydroformylation with Ru
3
(CO)
12
/1,10‐phenanthroline
Scheme 5.16 Hydroformylation using [HRu
3
(CO)
11
]
−
as catalyst.
Scheme 5.17 Hydroformylation of 1‐octene using K[Ru(III)EDTA(H
2
O)].
Scheme 5.18 Tandem hydroformylation–acetylation reaction to acetals.
Scheme 5.19 Alkoxycarbonylation of cyclic olefins.
Scheme 5.20 Methoxycarbonylation of 1‐butene using methanol as CO source....
Scheme 5.21 Methyoxycarbonylation of ethylene with methyl formate using [RuC...
Scheme 5.22 Methyoxycarbonylation of ethylene with methyl formate using Ru
3
(...
Scheme 5.23 Methoxycarbonylation with carbon dioxide.
Scheme 5.24 Paraformaldehyde as CO surrogate in the methoxycarbonylation of ...
Scheme 5.25 Metal‐catalyzed carbonylation of nitrobenzene to carbamate.
Scheme 5.26 (a) Synthesis of carbamate via palladium‐catalyzed carbonylation...
Scheme 5.27 Reaction mechanism of nitroarene carbonylation to carbamate.
Scheme 5.28 (a) An arylimido‐capped clusters as intermediate is proposed for...
Scheme 5.29 Synthesis of unsymmetrical urea from anilines and nitrobenzenes....
Scheme 5.30 Oxidative carbonylation of aniline to diphenylurea.
Scheme 5.31 (a) Ruthenium‐catalyzed carbonylation of piperidine. Source: Mod...
Scheme 5.32 (a) Carbonylation of alcohols to formates. (b) Carbonylation of ...
Scheme 5.33 (a) Hypothesized [2+2+1] intermolecular Pauson‐Khand reaction. (...
Scheme 5.34 (a) Intermolecular [2+2+1] Pauson‐Khand reaction with a removabl...
Scheme 5.35 (a) Hetero [2+2+1] Pauson‐Khand reactions giving lactones.. ...
Scheme 5.36 (a) 2‐Pyridyl ketone.and (b) α‐ketoester in the [2+2+1] hete...
Scheme 5.37 Ring‐closing metathesis and subsequent hetero‐Pauson–Khand react...
Scheme 5.38 [2+2+1] Hetero Pauson‐Khand reaction with (a) iminopyridines and...
Scheme 5.39 [4+1] Hetero‐Pauson–Khand reaction with imines.
Scheme 5.40 (a) [2+2+1+1] Cycloaddition of alkynes, norbornene and CO for th...
Scheme 5.41 (a) Carbonylative cyclization of allenyl alcohols to α,β‐unsatur...
Scheme 5.42 Ruthenium‐catalyzed Fischer–Tropsch synthesis using (a) high pre...
Scheme 5.43 Light‐induced FTS.
Scheme 5.44 Model of CO activation on the ruthenium nanoparticles.
Scheme 5.45 (a) Iodide‐promoted synthesis of methanol with syngas. (b) Forma...
Scheme 5.46 (a) The reaction Gibbs energy for the formation of ethylene glyc...
Scheme 5.47 Synthesis of acetic acid with a bimetallic Ru/Co catalyst.
Scheme 5.48 (a) Ru
3
(CO)
12
‐catalyzed reaction of syngas to lower alcohols (C
1
Scheme 5.49 (a) Homologation reaction from methanol to ethanol using Rh/Ru b...
Scheme 5.50 One‐pot reaction of MeOH and syngas leading to dimethoxymethane ...
Scheme 5.51 (a) The endothermic reverse water gas shift reaction in supporte...
Scheme 5.52 Homologation of methanol to ethanol using CO
2
and H
2
.
Scheme 5.53 (a) Synthesis of dimethoxymethane OME1 from CO
2
, H
2
, and MeOH. (...
Chapter 6
Scheme 6.1 (a) General hydroformylation reaction and (b) hydroformylation of...
Figure 6.1 Catalytic cycle for rhodium‐catalyzed propene hydroformylation....
Figure 6.2 TPPTS.
Figure 6.3 Aqueous biphase hydroformylation.
Scheme 6.2 Enantioselective hydroformylation (EHF).
Figure 6.4 Some chiral nonracemic ligands.
Scheme 6.3 Main examples of tandem reactions.
Scheme 6.4 Hydrohydroxymethylation of dicyclopentadiene.
Scheme 6.5 Synthesis of
N
‐arylated amines by hydroaminomethylation.
Scheme 6.6 Example of tandem hydroformylation/acyloin reaction.
Scheme 6.7 Tandem hydroformylation/Michael reaction of acrylates.
Scheme 6.8 Nonanenitrile synthesis by tandem hydroformylation/chemoenzymatic...
Scheme 6.9
Scheme 6.10 (a) Carbonylative dimerization of butyl acrylate.
Scheme 6.11 Hydroamidation of olefins.
Scheme 6.12 (a) Synthesis of cyclopentenones from 1,6‐ and 1,7‐enynes and CO...
Scheme 6.13 Rhodium-catalyzed carbonilative annulation of aniline.
Scheme 6.14 Carbonylation of aziridines and postulated reaction mechanism....
Scheme 6.15 Benzannulation for the synthesis of different heterocycles and p...
Scheme 6.16 Possible reaction mechanism for RhCl
3
-catalyzed alkoxycarbonylat...
Scheme 6.17 Reductive carbonylation of aryliodides.
Scheme 6.18 Carbonylative cycloaddition reaction.
Scheme 6.19 Example of benzo/[7+1] cycloaddition of cyclopropyl‐benzocyclobu...
Scheme 6.20 Reaction mechanism for oxidative cyclocarbonylation of ketimines...
Scheme 6.21 CO gas‐free cyclocarbonylation reaction of haloarenes.
Scheme 6.22 Hydroxymethyl furfural as CO surrogate and reagent in the carbon...
Scheme 6.23 C–H carboxylation of 2‐phenylaniline with CO
2
and reaction mecha...
Chapter 7
Scheme 7.1 Typical mechanism for palladium(0)‐catalyzed carbonylation reacti...
Scheme 7.2 Palladium‐catalyzed carbonylative synthesis of 2‐substituted‐4
H
‐3...
Scheme 7.3 Palladium‐catalyzed carbonylative synthesis of isocoumarins.
Scheme 7.4 Synthesis of thunberginol
A
.
Scheme 7.5 Palladium‐catalyzed carbonylation of aryl halides.
Scheme 7.6 Palladium‐catalyzed intramolecular cyclocarbonylation and intermo...
Scheme 7.7 Alkoxycarbonylation of aryl chlorides with primary alcohols.
Scheme 7.8 Plausible mechanism of alkoxycarbonylation of aryl chlorides with...
Scheme 7.9 Palladium‐catalyzed double carbonylative cyclization of benzoins....
Scheme 7.10 Palladium‐catalyzed enantioselective carbonylative Heck cyclizat...
Scheme 7.11 Synthesis of CRTH2 receptor antagonist.
Scheme 7.12 Palladium‐catalyzed carbonylation of 1‐azido‐2‐iodobenzenes with...
Scheme 7.13 Proposed reaction mechanism for carbonylation of 1‐azido‐2‐iodob...
Scheme 7.14 Synthesis of a bioactive 2‐aminobenzoxazine derivative.
Scheme 7.15 Pd
2
(dba)
3
catalyzed carbonylative synthesis of 2(5
H
)‐furanones....
Scheme 7.16 Pd(0)‐catalyzed carbonylation of (
Z
)‐2‐en‐4‐yn carbonates.
Scheme 7.17 Pd(0)‐catalyzed alkoxycarbonylation of propargylic mesylates....
Scheme 7.18 Palladium‐catalyzed enantiospecific carbonylative procedure for ...
Scheme 7.19 Gram‐scale enantiospecific synthesis of a nonracemic 2,3‐allenoa...
Scheme 7.20 Pd(0)‐catalyzed thiolative lactonization of internal alkynes....
Scheme 7.21 Pd/C‐catalyzed carbonylation with cinnamaldehydes as CO carrier....
Scheme 7.22 Palladium‐catalyzed carbonylative transformation of benzylamines...
Scheme 7.23 Synthesis of methylphenidate.
Scheme 7.24 Palladium‐catalyzed carbonylation of azirines.
Scheme 7.25 Palladium‐catalyzed carbonylation of allyl diethyl phosphate wit...
Scheme 7.26 Palladium‐catalyzed carbonylation of vinyl aziridines.
Scheme 7.27 The one‐pot multicomponent synthesis of β‐lactams.
Scheme 7.28 The synthesis of lactams via a tandem carbonylation/nitrogenatio...
Scheme 7.29 Palladium‐catalyzed intramolecular cyclization of 1‐butyl‐1‐(2‐i...
Scheme 7.30 Palladium‐catalyzed intermolecular aminocarbonylation/intramolec...
Scheme 7.31 Pd‐catalyzed carbonylation of α‐diazo carbonyl compounds or
N
‐to...
Scheme 7.32 Palladium‐catalyzed carbonylative cyclization reaction leading t...
Scheme 7.33 Palladium‐catalyzed aminocarbonylation of phenols.
Scheme 7.34 Proposed mechanism for aminocarbonylation of phenols.
Scheme 7.35 Pd/C catalyzed sulfoximinocarbonylation of aryl halides with NH‐...
Scheme 7.36 Palladium‐catalyzed carbonylative coupling of aryl chloride with...
Scheme 7.37 Plausible mechanism for palladium‐catalyzed carbonylative coupli...
Scheme 7.38 Pd/C‐catalyzed carbonylative transformation of aryl azides with ...
Scheme 7.39 Pd(0)‐catalyzed carbonylation‐coupling‐
endo
‐cyclization of α‐all...
Scheme 7.40 Proposed mechanism for carbonylation‐coupling
endo
‐cyclization o...
Scheme 7.41 Pd(0)‐catalyzed carbonylative cyclization of
N
‐
tert
‐butyl‐2‐(1‐a...
Scheme 7.42 Proposed mechanism for carbonylative cyclization leading to 3‐su...
Scheme 7.43 A straightforward route to 12‐acylindolo[1,2‐
c
]quinazolines. ...
Scheme 7.44 Palladium(0)‐catalyzed carbonylation of aryl iodides with trimet...
Scheme 7.45 Proposed mechanism for carbonylation of aryl iodides with trimet...
Scheme 7.46 Pd/C‐catalyzed carbonylative Suzuki–Miyaura cross‐coupling.
Scheme 7.47 Palladium‐catalyzed intermolecular arene C–H carbonylation.
Scheme 7.48 Palladium‐catalyzed carbonylative cyclization of
N
‐(2‐iodoaryl)e...
Scheme 7.49 Pd/C‐catalyzed carbonylation of aryl halides with 2‐hydroxyaceto...
Scheme 7.50 Palladium(0)‐catalyzed cascade carbonylation leading to β‐substi...
Scheme 7.51 Palladium‐catalyzed cyclocarbonylation of (2‐iodophenyl)hydrosil...
Scheme 7.52 Proposed reaction mechanism for the synthesis of benzosilinones ...
Scheme 7.53 Palladium‐catalyzed tandem enantioselective Heck/carbonylation d...
Scheme 7.54 Palladium‐catalyzed Heck‐type carbonylation of alkyl iodides. ...
Scheme 7.55 Pd/C‐catalyzed carbonylative reactions of aryl iodide to give es...
Scheme 7.56 Pd/Fe
3
O
4
catalyzed carbonylative Sonogashira coupling of aryl io...
Scheme 7.57 Carbonylative cascade reaction catalyzed by Pd@CN leading to pyr...
Scheme 7.58 Synthesis of P‐M‐NHC and M@CN.
Scheme 7.59 Pd(0)‐catalyzed dithiocarbonylation.
Scheme 7.60 Palladium‐catalyzed double carbonylation and cyclization reactio...
Scheme 7.61 Possible mechanism.
Scheme 7.62 Palladium‐catalyzed carbonylation of thioacetates and aryl iodid...
Scheme 7.63 Palladium‐catalyzed carbonylation of 5‐bromo‐furoic acid to cons...
Scheme 7.64 Regioselective dehydrative hydroxycarbonylation of propargylic a...
Scheme 7.65 Palladium‐catalyzed cyclocarbonylation to access thiadiazafluore...
Chapter 8
Scheme 8.1 Activation of different organic substrates by Pd(II) in carbonyla...
Scheme 8.2 Formation of carbonylated products from the organocarbonylpalladi...
Scheme 8.3 Pd(II)‐catalyzed oxidative carbonylation of cyclohexane to cycloh...
Scheme 8.4 Cu or Cu/Pd‐catalyzed oxidative carbonylation of methane to aceti...
Scheme 8.5 PdCl
2
‐catalyzed oxidative alkoxycarbonylation of ethane to benzyl...
Scheme 8.6 Pd(II)‐catalyzed oxidative allylic carbonylation of alkenes (BQ =...
Scheme 8.7 Pd(II)‐catalyzed oxidative alkoxycarbonylation of a substrate bea...
Scheme 8.8 Pd(II)‐catalyzed oxidative cyclocarbonylation of suitably substit...
Scheme 8.9 Stoichiometric Pd(II)‐mediated carbonylation of arenes and hetero...
Scheme 8.10 Carbonylation of benzene to benzophenone and of benzophenone to ...
Scheme 8.11 Pd(II)‐catalyzed oxidative alkoxycarbonylation of indoles at the...
Scheme 8.12 Pd(II)‐catalyzed oxidative
ortho
‐carbonylation of functionalized...
Scheme 8.13 Pd(II)‐catalyzed oxidative
ortho
‐alkoxycarbonylation of 2‐phenox...
Scheme 8.14 Pd(II)‐catalyzed oxidative
ortho
‐carbonylation of aromatic deriv...
Scheme 8.15 Synthesis of pyrroloquinazolinedione derivatives by Pd(II)‐catal...
Scheme 8.16 Pd(II)‐catalyzed oxidative carbonylation of suitably functionali...
Scheme 8.17 (a) Pd(II)‐catalyzed oxidative monoalkoxycarbonylation of olefin...
Scheme 8.18 Pd/C–CuI‐catalyzed oxidative monoalkoxycarbonylation of styrenes...
Scheme 8.19 Further CO insertion into the [(β‐alkoxycarbonyl)alkyl]palladium...
Scheme 8.20 Pd(II)‐catalyzed oxidative dialkoxycarbonylation of (a) simple α...
Scheme 8.21 Pd(II)‐catalyzed oxidative alkoxy‐alkoxycarbonylation of alkenes...
Scheme 8.22 Pd‐catalyzed additive alkoxycarbonylation (hydroesterification, ...
Scheme 8.23 Possible mechanisms in the Pd‐catalyzed additive alkoxycarbonyla...
Scheme 8.24 Palladium‐catalyzed additive carbonylation of tetramethylethylen...
Scheme 8.25 Pd(II)‐promoted alkoxy‐alkoxycarbonylation of 1,2‐dimethylcycloh...
Scheme 8.26 Pd‐catalyzed oxidative dialkoxycarbonylation of 1,3‐butadiene to...
Scheme 8.27 Pd‐catalyzed additive dialkoxycarbonylation of 1,3‐butadiene to ...
Scheme 8.28 (a) Pd‐promoted oxidative dialkoxycarbonylation [217] and (b) al...
Scheme 8.29 Synthesis of β,γ‐unsaturated esters by Pd‐catalyzed additive alk...
Scheme 8.30 Different mechanistic pathways in the Pd(II)‐catalyzed oxidative...
Scheme 8.31 Representative examples of the mechanistic pathways shown in Sch...
Scheme 8.32 Synthesis of 1‐aryl‐2‐(1‐tosylpyrrolidin‐2‐yl)ethan‐1‐ones by Pd...
Scheme 8.33 Pd(II)‐promoted oxidative cyclization–formylation or cyclization...
Scheme 8.34 Possible pathways in the Pd(II)‐catalyzed oxidative cyclocarbony...
Scheme 8.35 Representative examples of the mechanistic pathways shown in Sch...
Scheme 8.36 Possible mechanistic pathways in the Pd(II)‐catalyzed additive c...
Scheme 8.37 Synthesis of 1,4‐dihydroisoquinolin‐3(2
H
)‐ones by intramolecular...
Scheme 8.38 Formation of alkyl α‐(heteroaryl)acrylates by Pd(II)‐catalyzed o...
Scheme 8.39 Enantiospecific synthesis of methyl 2‐(1‐((
S
)‐1‐phenylethyl)pyrr...
Scheme 8.40 Pd(II)‐catalyzed oxidative cyclocarbonylation of allenols to 3‐c...
Scheme 8.41 Pd(II)‐catalyzed oxidative carbonylation of enallene derivatives...
Scheme 8.42 Main Pd(II)‐catalyzed oxidative carbonylations of alkynes: (a) d...
Scheme 8.43 PdI
2
/KI‐catalyzed oxidative dialkoxycarbonylation of terminal al...
Scheme 8.44 Pd(II)‐catalyzed oxidative dialkoxycarbonylation of internal alk...
Scheme 8.45 Synthesis of (a) maleic acids and (b) maleic anhydrides by PdI
2
/...
Scheme 8.46 Tsuji's oxidative monoalkoxycarbonylation of terminal alkynes to...
Scheme 8.47 An example of Pd(II)‐catalyzed oxidative monoalkoxycarbonylation...
Scheme 8.48 PdI
2
/KI‐catalyzed oxidative monoaminocarbonylation of terminal a...
Scheme 8.49 Regiodivergent methoxycarbonylation reactions of phenylacetylene...
Scheme 8.50 Possible mechanisms in the Pd‐catalyzed additive alkoxycarbonyla...
Scheme 8.51 Pd(II)‐catalyzed additive aminocarbonylation of terminal alkynes...
Scheme 8.52 Formation of succinate esters by sequential double additive alko...
Scheme 8.53 Synthesis of (
E
)‐4‐(1
H
‐indol‐3‐yl)‐4‐oxobut‐2‐enoates by Pd(II)‐...
Scheme 8.54 Combined Pd(II)‐catalyzed oxidative carbonylation and reductive ...
Scheme 8.55 Reductive carbonylation of terminal alkynes to 2(5
H
)‐furanones u...
Scheme 8.56 Pd‐catalyzed hydroformylation of alkynes to α,β‐unsaturated alde...
Scheme 8.57 Multiple pathways in the oxidative carbonylation of acetylenic s...
Scheme 8.58 Synthesis of ζ‐lactams with antitumor activity by PdI
2
/KI‐cataly...
Scheme 8.59 Sequential PdI
2
/KI‐catalyzed oxidative monoaminocarbonylation–in...
Scheme 8.60 Auto‐tandem catalysis leading to oxazolidinones from propargyl a...
Scheme 8.61 Synthesis of imidazothiazinones by PdI
2
/KI‐catalyzed sequential ...
Scheme 8.62 Pd(II)‐catalyzed oxidative
exo
and
endo
cyclization–carbonylatio...
Scheme 8.63 Synthesis of isobenzofuranimine derivatives by PdI
2
/KI‐catalyzed...
Scheme 8.64 PdI
2
/KI‐catalyzed oxidative cyclization–alkoxycarbonylation–dehy...
Scheme 8.65 PdI
2
/KI‐catalyzed oxidative sequential carboxylation–cyclization...
Scheme 8.66 Synthesis of isobenzofuranone derivatives by PdI
2
/KI‐catalyzed o...
Scheme 8.67 Sequential PdI
2
/KI‐catalyzed oxidative monoaminocarbonylation–in...
Scheme 8.68 Sequential PdI
2
/KI‐catalyzed monoaminocarbonylation–intramolecul...
Scheme 8.69 Pd(II)‐catalyzed cyclization–carbonylation–cyclization coupling ...
Scheme 8.70 Synthesis of di(1
H
‐pyrazol‐4‐yl)ketones by the CCC coupling appr...
Scheme 8.71 Examples of PdI
2
/KI‐catalyzed oxidative carbonylative double cyc...
Scheme 8.72 Synthesis of ɛ‐lactams by Pd(II)‐catalyzed intramolecular additi...
Scheme 8.73 Pd(II)‐catalyzed Pauson–Khand reaction, leading to cyclopentenon...
Scheme 8.74 Combination between triple‐bond oxidative dialkoxycarbonylation ...
Scheme 8.75 Synthesis of diethyl (
E
)‐2‐(ethoxymethylene)succinate by formal ...
Scheme 8.76 Synthesis of benzofuran derivatives by sequential homobimetallic...
Scheme 8.77 Pd(II)‐catalyzed oxidative carbonylation processes of alcohols a...
Scheme 8.78 Mechanistic pathways for the formation of carbonates and oxalate...
Scheme 8.79 Synthesis of cyclic carbonates by PdI
2
/KI‐catalyzed oxidative ca...
Scheme 8.80 PdI
2
/KI‐catalyzed oxidative carbonylation of (a) primary amines ...
Scheme 8.81 (a) Synthesis of carbamates by Pd(OAc)
2
/KI‐catalyzed oxidative a...
Scheme 8.82 (a) Mechanism of the palladium‐catalyzed direct and substitutive...
Chapter 9
Figure 9.1 SZ structure.
Scheme 9.1 SZ‐ and zirconia‐catalyzed Gatterman–Koch reaction.
Scheme 9.2 SZ‐catalyzed isobutane carbonylation.
Scheme 9.3
n
‐Pentane carbonylation on SZ.
Scheme 9.4 Propane carbonylation on SZ.
Figure 9.2 General structure of zirconacycles.
Scheme 9.5 First example of carbonylation of zirconacyclic structure.
Figure 9.3 Synthesis of Negishi reagent.
Scheme 9.6 Carbonylation reaction via Negishi reagent: general behavior.
Scheme 9.7 Carbonylation of nonterminal enynes.
Scheme 9.8 Application of the zirconocene‐promoted bicyclization–carbonylati...
Scheme 9.9 Zirconium‐promoted intermolecular coupling of disubstituted alkyn...
Scheme 9.10 Zirconium‐promoted alkene intermolecular coupling.
Scheme 9.11 Zirconocene‐promoted bicyclization–carbonylation of dienes.
Scheme 9.12 Example of zirconocene‐promoted bicyclization–carbonylation of d...
Scheme 9.13 Reaction of zirconacyclopentadienes derived from two alkynes wit...
Scheme 9.14 Proposed reaction mechanism.
Scheme 9.15 Synthesis of cyclopentadienones.
Scheme 9.16 Double carbonylation of zirconocene–alkyne complexes.
Scheme 9.17 Carbonylation of zirconacycle formally derived from terminal alk...
Scheme 9.18 Reaction scope.
Scheme 9.19 Carbonylation of alcohols by solid superacids.
Scheme 9.20 Carbonylation of methoxymethyl chloride with AgSbF
6
.
Scheme 9.21 Pd/Ag as synergic catalysts for the tandem CO functionalization ...
Scheme 9.22 Control experiments and reaction mechanism.
Scheme 9.23 Reaction scope.
Scheme 9.24 Mo(CO)
6
‐promoted carbonylation of alkyl halides: synthesis of es...
Scheme 9.25 Ethylene carbonylation with Mo(CO
6
).
Scheme 9.26 Flow production of methyl formate via formal carbonylation of me...
Scheme 9.27 Molybdenum‐promoted carbamoylation of aryl halides.
Scheme 9.28 Scope of catalytic Mo(CO)
6
‐mediated carbamoylation reaction.
Scheme 9.29 Scope: primary amides synthesis.
Scheme 9.30 Alkoxycarbonylation of aryl halides with a low loading of Mo(CO)
Scheme 9.31 Mo‐mediated carbonylation of aryl halides under microwave irradi...
Scheme 9.32 Intermolecular molybdenum carbonyl promoted formation of ketones...
Scheme 9.33 Intramolecular acylmolybdenum addition to alkenes.
Scheme 9.34 Reaction mechanism.
Scheme 9.35 Molybdenum‐mediated cyclocarbonylation of allenyl compounds.
Scheme 9.36 Molybdenum‐mediated cyclocarbonylation of 1‐ethynyl‐2‐allenyl be...
Scheme 9.37 DBU‐mediated amino‐ and amidocarbonylation of aryl iodides and b...
Scheme 9.38 DBU‐mediated amino‐ and amidocarbonylation: synthesis of targets...
Scheme 9.39 Mo‐promoted CO functionalization of sulfonyl azides.
Scheme 9.40 Pd‐catalyzed Mo(CO)
6
‐promoted carbonylative Sonogashira/cyclizat...
Scheme 9.41 Nucleophiles used in cascade Pd‐catalyzed Mo(CO)
6
‐promoted carbo...
Scheme 9.42 Intramolecular C(sp
2
)–halogen carbonylation.
Scheme 9.43 Mo(CO)
6
‐promoted carbonylative intramolecular cyclizations via C...
Scheme 9.44 Mo(CO)
6
‐promoted Hiyama and Negishi cross‐coupling.
Scheme 9.45 Mo(CO)
6
‐promoted carbonylative Suzuki–Miyaura cross‐coupling.
Scheme 9.46 Mo(CO)
6
‐promoted carbonylative Stille coupling reactions.
Scheme 9.47 Ni‐catalyzed Mo(CO)
6
‐promoted carbonylative coupling reactions....
Chapter 10
Scheme 10.1 Migratory CO insertion.
Scheme 10.2 Catalytic cycle for Rh‐catalyzed methanol carbonylation.
Scheme 10.3 Catalytic cycles for iridium‐catalyzed methanol carbonylation an...
Scheme 10.4 Iodide loss mechanism for stoichiometric carbonylation of [Ir(CO...
Scheme 10.5 Proposed CO‐loss mechanism for photochemical carbonylation of [I...
Scheme 10.6 Proposed mechanism for methane formation from Ir(III) acetyl spe...
Figure 10.1 Comparison of methanol carbonylation rates as a function of wate...
Scheme 10.7 Mechanism for iridium‐catalyzed methanol carbonylation with a ru...
Scheme 10.8 Proposed steps in Ir‐La/C‐catalyzed methanol carbonylation (s = ...
Scheme 10.9 Stoichiometric reaction steps for iridium pincer‐crown ether com...
Scheme 10.10 Hydroformylation of an alkene to give linear and branched aldeh...
Scheme 10.11 General hydroformylation mechanism for group 9 metal catalysts ...
Scheme 10.12 Ir‐propionyl complexes of diphosphines dppe (a), xantphos (b), ...
Scheme 10.13 Simplified mechanism for Pt/SnCl
2
‐catalyzed alkene hydroformyla...
Scheme 10.14 Hydroxycarbonylation (R = H) or methoxycarbonylation (R = Me) o...
Scheme 10.15 Mechanism for Pd or Pt diphosphine‐catalyzed methoxycarbonylati...
Scheme 10.16 Ir‐catalyzed reactions of alkynes: (a) intramolecular Pauson–Kh...
Scheme 10.17 Proposed mechanism for tungsten‐catalyzed oxidative carbonylati...
Scheme 10.18 Proposed mechanism for oxidative carbonylation of methanol cata...
Chapter 11
Scheme 11.1 Conversion of organohalides into aldehydes by free‐radical carbo...
Scheme 11.2 Radical carbonylations of
gem
‐dihalocyclopropane derivatives wit...
Scheme 11.3 Radical‐mediated double carbonylations of alk‐4‐enyl iodides....
Scheme 11.4 Free‐radical carbonylation of organoiodides, carbon monoxide, an...
Scheme 11.5 CO‐trapping reaction under thermolysis of alkoxyamines.
Scheme 11.6 Visible‐light‐induced radical carbonylation of aryldiazonium sal...
Scheme 11.7 Visible‐light‐induced radical carbonylation of arylsulfonyl chlo...
Scheme 11.8 Carbonylation of alkyl radicals derived from organosilicates....
Scheme 11.9 Deaminative carbonylative coupling of alkylamines with styrenes....
Scheme 11.10 Atmospheric‐pressure carbonylative Suzuki reactions of aryl hal...
Scheme 11.11 Iodide‐mediated domino carbonylation–benzylation of benzyl chlo...
Scheme 11.12 Iodide‐mediated domino carbonylation–benzylation of benzyl chlo...
Scheme 11.13 (a) Carbonylative Suzuki couplings of aryl halides with arylbor...
Scheme 11.14 Synthesis of Fenofibrate by transition metal‐free carbonylative...
Scheme 11.15 Radical‐mediated double carbonylation of alk‐4‐enyl iodides for...
Scheme 11.16 Ester synthesis from alkyl iodides, carbon monoxide, and alcoho...
Scheme 11.17 Five‐ to seven‐membered ring lactones synthesis from ω‐hydroxya...
Scheme 11.18 Transition metal‐free alkoxycarbonylation of aryl halides.....
Scheme 11.19 Transition metal‐free and radical initiator‐free alkoxycarbonyl...
Scheme 11.20 Radical alkoxycarbonylation of aryldiazonium salts through visi...
Scheme 11.21 Visible‐light photoredox‐catalyzed radical alkoxycarbonylation ...
Scheme 11.22 HCOONa‐mediated radical alkoxycarbonylation of aryldiazonium te...
Scheme 11.23 Oxidative alkoxycarbonylation of alkanes.
Scheme 11.24 Carbonylation of alkyl allyl sulfones with phenyl benzenethiosu...
Scheme 11.25 Carbonylation of alkyl allyl sulfones with phenyl benzenethiosu...
Scheme 11.26 Carbonylation of alkyl iodides with primary and secondary amine...
Scheme 11.27 Carbonylation of aryl iodides with primary and secondary amines...
Scheme 11.28 Carbonylation of aryl iodides with primary and secondary amines...
Scheme 11.29 Oxidative carbonylation of methane and ethane.
Scheme 11.30 Hydroxycarbonylation of aryl iodides.
Scheme 11.31 Carbonylation of aryl iodides for carboxylic acid anhydride syn...
Scheme 11.32 Carbonylation of alkane for acid chloride synthesis.
Scheme 11.33 Hydroxymethylation of organic bromides.
Scheme 11.34 Hydroxymethylation of organic bromides.
Scheme 11.35 Hydroxymethylation of organohalides.
Guide
Cover
Table of Contents
Title Page
Copyright
Dedication
Preface
Begin Reading
Index
WILEY END USER LICENSE AGREEMENT
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Carbon Monoxide in Organic Synthesis
Carbonylation Chemistry
Edited byBartolo Gabriele
Editor
Prof. Bartolo GabrieleUniversity of CalabriaDepartment of Chemistry & Chemical TechnologiesVia Pietro Bucci 12/C87036 Arcavacata di Rende (CS)Italy
Cover Image: © azatvaleev/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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© 2022 WILEY‐VCH GmbH, Boschstr. 12, 69469 Weinheim, Germany
All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.
Print ISBN: 978‐3‐527‐34795‐7ePDF ISBN: 978‐3‐527‐82933‐0ePub ISBN: 978‐3‐527‐82934‐7oBook ISBN: 978‐3‐527‐82935‐4
This book is dedicated to the memory of my beloved parents, Giuseppe Gabriele and Anna La Valle.
Preface
This book is dedicated to the use of carbon monoxide as a C‐1 building block in organic synthesis. The incorporation of carbon monoxide into an organic substrate to give a carbonyl compound is called “carbonylation.” Carbonylation reactions, discovered in 1930s thanks to the pioneering work by Roelen and Reppe, are now established as a most powerful methodology for the direct synthesis of carbonyl derivatives using the simplest and readily available C‐1 unit. Impressive progress has been made in this field at both industrial and academic levels, so nowadays carbonylations are widely applied not only for the production of industrially relevant, relatively simple carbonyl compounds but also for the preparation of complex molecular architectures and even as key steps in natural product synthesis.
I have been involved in this fascinating area of research for many years, with particular interest in palladium‐catalyzed processes. After my degree in chemistry at the University of Calabria with a thesis on Pd(II)‐catalyzed alkyne carbonylation (1990), in 1991, I joined the group of Professors Gian Paolo Chiusoli and Mirco Costa at the University of Parma for a research stage. At that time, the use of CO as C‐1 unit in synthesis was among the primary research interests of Professors Chiusoli and Costa, and I was very happy to be involved in this emerging research area. Since then, I continued to work in this field during my PhD (at the University of Calabria, with Professor Giuseppe Salerno) and then in the course my independent career.
Therefore, at the end 2019, when Dr. Anne Brennführer invited me to submit a book proposal on carbonylation chemistry for Wiley‐VCH, I was very happy to accept. I was aware that other important and excellent books had been published before (the most recent one in 2014). However, I was convinced that a new updated book in this field, organized in a different way with respect to those already published, could be useful to the scientific community. In fact, a new book could be of interest not only for those researchers directly involved in carbonylation chemistry (from both academia and industry) but also for researchers, postdocs, and PhD students interested in the most recent trends in organic synthesis.
Most carbonylation processes are catalyzed by transition metal species. Different from the previous books on carbonylations, which were organized on the basis of the process type or the nature of the carbonylated product obtained, this book has been structured according to the metal promoting the carbonylation process. The aim of this kind of classification was to help the reader to better focus on the catalytic abilities and specificities of different metal catalysts in promoting various kinds of carbonylations. However, considering the increasing importance of metal‐free carbonylation reactions (radical carbonylations, in particular), a final chapter has been also devoted to this emerging area of research.
The book contributors are leading scientists in the field, who have kindly accepted my invitation to spend some of their time for the realization of this exciting project, and I extend my warmest thanks to them. I also would like to thank very much the Wiley‐VCH editors, in particular Dr. Anne Brennführer and Ms. Katherine Wong, for the kind invitation to edit this book and for their invaluable cooperation and support throughout the entire preparation of the book.
I hope you will enjoy reading the book at least as much as I have enjoyed in editing it!
Arcavacata di Rende (CS)January 18, 2021
Bartolo Gabriele
1Introduction: Carbon Monoxide as Synthon in Organic Synthesis
Bartolo Gabriele
University of Calabria, Laboratory of Industrial and Synthetic Organic Chemistry (LISOC), Department of Chemistry and Chemical Technologies, Via Pietro Bucci 12/C, 87036 Arcavacata di Rende, Italy
This book discusses the synthesis of carbonylated compounds by introducing the carbonyl function into an organic substrate (carbonylation) employing the simplest C‐1 unit as carbonylating agent, carbon monoxide. Carbon monoxide is a largely available feedstock. It is produced industrially by partial oxidation of petroleum hydrocarbons and steam reforming of light hydrocarbons (including natural gas) or gasification of coal to give syngas (CO and H2) [1]. In the future, it is expected that a growing amount of carbon monoxide will be available from renewable feedstocks, such as biowastes and CO2 [2]. CO is also the simplest unit that, upon insertion into an organic substrate, can be directly transformed, without atom loss, into a carbonyl group. It is therefore a desirable and useful building block in synthesis to produce high value‐added industrially relevant molecules and fine chemicals.
Carbonylation reactions were disclosed in the 1930s by the seminal works of Roelen [3] and Reppe [4] (who also coined the term “carbonylation”) for industrial applications. Since then, the scientific progress in this field has been enormous, thanks, in particular, to the development of more and more selective and efficient catalysts. These catalysts are able to promote a plethora of carbonylations under mild conditions, which can be applied to a large variety of organic substrates. Accordingly, carbonylations with CO have become increasingly more and more important, at the industrial and academic level, as testified by the considerable number of books [5–12] and reviews [13–115] dedicated to this topic and by the increasing number of industrial patents and scientific publications.
As said above, the incorporation of carbon monoxide into an organic substrate to give a carbonyl compound is called carbonylation. Interestingly, during the last years, considerable effort has been made by the scientific community to use CO surrogates as indirect carbonylating agents or as in situ sources of CO (both in industry and in academia, to avoid the direct handling of gaseous and toxic CO). In this book, several representative examples of CO surrogates will also be presented and discussed. Although CO surrogates can be interesting from a practical point of view, it should still be considered that carbon monoxide is cheaper than its surrogates and that carbonylations with CO occur with a higher atom economy.
Carbon monoxide possesses the strongest bond currently known (257.3 kcal/mol) [116]. This bond is only weakly polarized in the direction of carbon (the experimental dipole moment is 0.122 D) [117]. These characteristics make carbon monoxide a relatively stable and inert molecule. Consequently, CO can be attacked by highly reactive species, such as free radicals, carbocations, and strong nucleophiles (like alkoxides, amide anions, and organolithium reagents) (Scheme 1.1). These reactions form acyl radicals, acyl carbocations, and [NuCO]− intermediates (alkoxycarbonyl anions, carbamoyl anions, and acyl anions). They evolve toward forming the final carbonylation product depending on the nature of reactants and reaction conditions (Scheme 1.1).
Scheme 1.1 Reactions of carbon monoxide with free radicals, carbocations, or strong nucleophiles (such as RO−, R2N−, RLi).
However, the most common way to activate CO in carbonylation reactions under relatively mild conditions is metal coordination. In fact, upon coordination to a metal center M, the carbon atom becomes more electrophilic. It accordingly becomes susceptible to attack even by a relatively weak nucleophile, either external or coordinated to the metal (Scheme 1.2; formal charges are omitted for clarity). When occurring within the coordination sphere of the metal, this process is called migratory insertion. In this case, the metal also favors the attack to coordinated CO for entropic reasons. In either case (external attack, Scheme 1.2a, or migratory insertion, Scheme 1.2b), the coordinated carbon monoxide is transformed into a species in which the carbonyl group is bonded to M, and whose particular structure depends, apart from the metal, on the nature of the nucleophile. Thus, if the nucleophilic species is a carbon group (alkyl, alkenyl, or aryl) σ‐bonded to the metal undergoing migratory insertion, an acyl‐ or aroyl‐metal species is formed. On the other hand, oxygen and nitrogen nucleophiles will lead to hydroxycarbonyl‐, alkoxycarbonyl‐, or carbamoyl‐metal complexes, respectively (Scheme 1.2).
Scheme 1.2 Carbon monoxide coordinated to a metal center becomes more susceptible to nucleophilic attack, either intermolecularly (a) or intramolecularly (migratory insertion) (b).
These intermediates' fate will depend on the nature of the metal and of the reactants taking part in the carbonylation process and on reaction conditions. In most cases, the final carbonylated organic product is formed with the release of the metal, either in its original or in a different oxidation state. In the first case, a catalytic cycle is directly attained. In contrast, in the second case, the metal species must be reported in its original oxidation state (using a suitable redox agent) to achieve a catalytic process. For example, an acyl‐ or aroyl‐metal intermediate R(CO)–M[+n]–X (X− = halide or other ligands, with M in the oxidation state [+n]) may undergo a nucleophilic attack by a nucleophile NuH (like water, alcohol, or an amine), with the formation of the carbonylated product R(CO)Nu (such as a carboxylic acid, an ester, or an amide), HX, and the reduced metal M[+(n−2)] (reductive displacement or nucleophilic displacement; Scheme 1.3).
Scheme 1.3 An acyl‐ or aroyl‐metal intermediate (R = carbon group) undergoing reductive displacement (also called nucleophilic displacement).
If the metal initiated the process in its [+(n−2)] oxidation state (for example, by oxidative addition of R–X to the metal center to give R–M[+n]–X followed by CO migratory insertion), a catalytic cycle is directly achieved (Scheme 1.4). On the other hand, if the metal initiated the process in its [+n] oxidation state (for example, by metalation of R–H by M[+n]X2 with the formation of R–M[+n]–X + HX, followed by CO migratory insertion), the use of a suitable external oxidant is necessary to reconvert the reduced metal M[+(n−2)] to M[+n] and realize a catalytic process (Scheme 1.5). Clearly, from a practical and economical point of view, the occurrence of a carbonylative catalytic cycle is highly desirable. In the last decades, there has been considerable attention to developing more and more robust and efficient metal catalysts, also heterogeneous and/or with the possibility of being effectively recycled.
Scheme 1.4 An example of catalytic carbonylation process in which the metal is eliminated at the end of the process in its original oxidation state.
Scheme 1.5 An example of catalytic carbonylation process in which the metal is reduced at the end of the process and is reoxidized to its original oxidation state by the action of an external oxidant.
The nucleophilic attack of NuH to an acyl‐ or aroyl‐metal intermediate (either inter‐ or intramolecular) is a common and important process by which the final carbonylated compound is delivered in a carbonylation reaction. This process is called reductive displacement or nucleophilic displacement. The exact mechanism this step may take place depends on reaction conditions, and, in particular, if the carbonylation process is done under acidic, neutral, or basic conditions. Under acidic and neutral conditions, the nucleophile tends to attack the carbonyl (possibly protonated) of the R(CO)–M[+n]–X complex, with the formation of a tetrahedral intermediate. This intermediate undergoes β‐H elimination from the H–O–C–MX moiety to give R(CO)Nu and a metal hydride species H–M[+n]–X, in equilibrium with M[+(n−2)] + HX (addition–elimination mechanism, Scheme 1.6a). On the other hand, under basic conditions, NuH (possibly in its anionic Nu− form) preferably attacks the metal center, with formal elimination of X− and formation of the R(CO)–M[+n]–Nu complex. Reductive elimination then leads to R(CO)Nu and M[+(n−2)] (ligand exchange mechanism; Scheme 1.6b). This latter case also occurs when the R(CO)–M[+n]–X species is attacked by an organometallic reagent R′M′ with the formation of M′X and R(CO)–M[+n]–R′ that undergoes reductive elimination to give R(CO)R′ (as occurs in the so‐called carbonylative cross‐coupling reactions) (transmetalation mechanism; Scheme 1.6c).
Scheme 1.6 Possible mechanistic pathways in the nucleophilic displacement step: (a) nucleophilic attack to the carbonyl followed by β‐H elimination from the H–O–C–MX unit (addition–elimination mechanism); (b) nucleophilic attack to the metal center followed by reductive elimination (ligand exchange mechanism); (c) reaction with an organometallic reagent R′M′ followed by reductive elimination (transmetalation mechanism).
Depending on the exact stoichiometry of the process, carbonylations can be broadly classified into direct, substitutive, additive, oxidative, and reductive carbonylations. In direct carbonylation, carbon monoxide is formally inserted into an AB bond of an organic substrate to give a carbonylated product bearing the A(CO)B functionality (Scheme 1.7a). An example is the direct catalytic carbonylation of methanol to acetic acid (Scheme 1.7b), a particularly important industrial process.
Scheme 1.7 A generic direct carbonylation process (a) and direct carbonylation of methanol to acetic acid (b).
On the other hand, substitutive carbonylation corresponds to the formal substitution of a certain functional group W of an organic substrate with a carbonylic functional group (CO)Z (Scheme 1.8a). An example is given by the substitutive carbonylation of an allyl alcohol RCH<span class="dbond"></span>CHCH2OH carried out with CO and an alcohol (R′OH) to give a β,γ‐unsaturated ester with water as coproduct, as shown in Scheme 1.8b.
Scheme 1.8 A generic substitutive carbonylation process (a) and substitutive carbonylation of allyl alcohols to β,γ‐unsaturated esters (b).
Additive carbonylation is a process in which carbon monoxide, together with an H–Y species (Y = hydrogen or a nucleophilic group), adds to an unsaturated carbon–carbon bond, as exemplified in Scheme 1.9a for the double bond. Examples are given by the hydroformylation of olefins (in which Y = H, with the formal addition to the double bond of a hydrogen atom on one carbon and the formyl group on the other one, Scheme 1.9b) or the Reppe alkoxycarbonylation of an olefin with CO and an alcohol (Y = OR′, with the formal addition to the double bond of a hydrogen atom on one carbon and the alkoxycarbonyl group on the other one, Scheme 1.9c).
Scheme 1.9 A generic additive carbonylation process for an olefin (a), additive carbonylation of an olefin with H2 (hydroformylation) (b), and additive carbonylation of an olefin with an alcohol (Reppe carbonylation) (c).
In an oxidative carbonylation reaction, the process occurs with the formal simultaneous elimination of molecular hydrogen from the substrate(s) (Scheme 1.10a). Although a few examples are known in the literature in which molecular hydrogen is indeed formed as the reaction coproduct, in the majority of the cases, the process, promoted by a metal catalyst M[+n], occurs with simultaneous reduction of the metal by two units and with the concomitant formation of 2 mol of H+ (Scheme 1.10b). A process like this is not catalytic unless a suitable external oxidant (able to reconvert the reduced metal into its original oxidation state, Scheme 1.10c) is added among the reactants (Scheme 1.10d). An example is the PdI2‐catalyzed oxidative dialkoxycarbonylation of alkynes to give maleic diesters carried out with molecular oxygen as the external oxidant, as shown in Scheme 1.11.
Scheme 1.10 A generic oxidative carbonylation process (a) with the elimination of molecular hydrogen from substrate(s) SH2 and formation of carbonylated product(s) S(CO) or (b) with reduction by two units of a metal species promoting the process or (d) carried out in the presence of an external oxidant, able to reconvert the promoting metal in its original oxidation state (c). The combination between the stoichiometric process (b) with metal reoxidation (c) gives the reaction (d) catalytic in the metal.
Scheme 1.11 PdI2‐catalyzed oxidative dialkoxycarbonylation of alkynes to maleic diesters. The catalytic process is the result of the combination between the dialkoxycarbonylation process occurring with reduction of PdI2 to Pd(0) followed by reoxidation of Pd(0) to PdI2 by the action of the external oxidant (molecular oxygen).
On the other hand, reductive carbonylation is when molecular hydrogen is formally inserted together with CO into the organic reactant(s) (Scheme 1.12a). The hydroformylation reaction of olefins, shown in Scheme 1.9b, is the most important example in which molecular hydrogen is used as a coreactant. A more complex example is given by the reductive carbonylation of alkynes, in which molecular hydrogen is formally released from the water‐shift reaction (CO + H2O → CO2 + H2) and reduces one carbonyl unit into a –CH2O– moiety within the final unsaturated γ‐lactone ring (Scheme 1.12b).
Scheme 1.12 (a) A generic reductive carbonylation process with molecular hydrogen as reducing agent and (b) reductive carbonylation of alkynes to furan‐2(5H)‐ones (in which H2 is formally produced in situ by the water‐shift reaction, CO + H2O → CO2 + H2).
The major emphasis of the book is based on the increasing importance and versatility of transition metal‐catalyzed carbonylation processes. The book represents the first attempt to present carbonylations based on the kind of metal promoting the carbonylation process rather than on the carbonylation process type or the carbonylated product's nature. Part I of the book deals with carbonylations promoted by first‐row transition metal catalysts (cobalt, nickel, manganese, iron, copper). Part II describes carbonylations promoted by second‐row transition metal catalysts (ruthenium, rhodium, palladium, other second‐row metals). Carbonylation promoted by third‐row transition metal catalysts is discussed in Part III. Chapter 11 is also devoted to metal‐free carbonylation processes.
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