Abundant metal-catalyzed carbonylation of alkyl bromides and alkyl chlorides

Gu, Xing-Wei; Wu, Xiao‐Feng

doi:10.1039/d3qo00158j

Cited by 6 publications

(1 citation statement)

References 33 publications

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“…It is noteworthy that although the carbonylation of unactivated alkyl electrophiles has been previously reviewed in the literature, it has always been as part of a discussion with other reactions, [ 12 ] specified to limited substrates, [ 13 ] or merely focused on copper catalysis. [ 14 ] The literature specially summarizing base‐ metal‐catalyzed carbonylation of unactivated alkyl electrophiles is still imperative, considering the significance and rapid development of this research field in recent years.…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in Base‐Metal‐Catalyzed Carbonylation of Unactivated Alkyl Electrophiles^†

Jiang

Chen

et al. 2023

Chin. J. Chem.

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Comprehensive SummaryTransition metal‐catalyzed carbonylation reactions represent a direct and atom‐economical approach to synthesize carbonyl compounds or their derivatives by using CO as a cheap and readily available C1 feedstock. While carbonylation of C(sp2)‐hybridized electrophiles (e.g. aryl halides) is well developed, carbonylation of less reactive unactivated alkyl electrophiles remains challenging. Recently, the use of earth‐abundant base metals including Cu, Co, Mn, Fe, Ni as catalysts has enabled advances in carbonylative coupling of alkyl electrophiles for approaching diverse carbonyl compounds or their derivatives, notably, some of which are of synthetic importance but difficult to be synthesized through previous reported methods. Herein, we have summarized and discussed these recent achievements in base‐metal‐catalyzed carbonylative C–C, C–N, C–O, C–X coupling and other carbonylation reactions of unactivated alkyl electrophiles using CO as C1 source.This article is protected by copyright. All rights reserved.

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Section: Introductionmentioning

confidence: 99%

Recent Advances in Base‐Metal‐Catalyzed Carbonylation of Unactivated Alkyl Electrophiles^†

Jiang

Chen

et al. 2023

Chin. J. Chem.

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Carbonylation Reactions of a Metallapentalyne: Synthesis of Its Ester and Amide Derivatives

Zhu,

Chen,

Luo

et al. 2024

Chin. J. Chem.

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Comprehensive SummaryCarbonylation reactions are a valuable synthetic method to construct carbonyl compounds and carbonylation reactions of aryl halides stand out as a highly significant tool for generating carbonyl substituted arenes. However, the important reactions have never been realized in aromatic metallacycles. Herein, we present the first carbonylation reactions of metallaaromatics, specifically alkoxycarbonylation and aminocarbonylation reactions of an osmapentalyne. During the carbonylation process, the electronic and steric properties of nucleophiles are regarded as critical factors. The alcohols with bulky substituents (isopropanol) require more reaction time and tert‐butyl alcohol is inert in the reaction. Comparatively, amines, being stronger nucleophiles, exhibit divergent behaviors. Bulky amines undergo aminocarbonylation, whereas small amines prefer direct nucleophilic additions. Control experiments revealed that the intermediate derived from coupling of metal carbyne with CO plays a significant role in the carbonylation reaction. According to these observations, a divergent pathway for the reaction is proposed. Furthermore, the photophysical properties of these carbonyl‐functionalized osmapentalene complexes are studied, and the maximum absorption peak of compound with a carboxylic group exhibits a significant red‐shift due to the smaller HOMO‐LUMO gap. These findings contribute to expanding the reactivity of metallaaromatics and offer new opportunities for the synthesis of carbonyl‐functionalized metallacycles.

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Carbonylative transformation of aryl halides and strong bonds via cheap metal catalysts and sustainable technologies

Yang,

Liu,

et al. 2024

Green Synthesis and Catalysis

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Abundant metal-catalyzed carbonylation of alkyl bromides and alkyl chlorides

Abstract: Transition metal-catalyzed carbonylation of alkyl halides is one of the most efficient methods for the assembly of aliphatic carbonyl-containing compounds. Despite the long history of carbonylation chemistry, core breakthroughs are...

Cited by 6 publications

References 33 publications

Recent Advances in Base‐Metal‐Catalyzed Carbonylation of Unactivated Alkyl Electrophiles^†

Recent Advances in Base‐Metal‐Catalyzed Carbonylation of Unactivated Alkyl Electrophiles^†

Carbonylation Reactions of a Metallapentalyne: Synthesis of Its Ester and Amide Derivatives

Carbonylative transformation of aryl halides and strong bonds via cheap metal catalysts and sustainable technologies

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Abundant metal-catalyzed carbonylation of alkyl bromides and alkyl chlorides

Abstract: Transition metal-catalyzed carbonylation of alkyl halides is one of the most efficient methods for the assembly of aliphatic carbonyl-containing compounds. Despite the long history of carbonylation chemistry, core breakthroughs are...

Cited by 6 publications

References 33 publications

Recent Advances in Base‐Metal‐Catalyzed Carbonylation of Unactivated Alkyl Electrophiles†

Recent Advances in Base‐Metal‐Catalyzed Carbonylation of Unactivated Alkyl Electrophiles†

Carbonylation Reactions of a Metallapentalyne: Synthesis of Its Ester and Amide Derivatives

Carbonylative transformation of aryl halides and strong bonds via cheap metal catalysts and sustainable technologies

Contact Info

Product

Resources

About

Recent Advances in Base‐Metal‐Catalyzed Carbonylation of Unactivated Alkyl Electrophiles^†

Recent Advances in Base‐Metal‐Catalyzed Carbonylation of Unactivated Alkyl Electrophiles^†