Copper-catalyzed carbonylative multi-component borylamidation of alkenes for synthesizing γ-boryl amides with CO as both methylene and carbonyl sources.

A multi-component carbonylation reaction is an efficient strategy for the synthesis of valuable carbonyl compounds from simple and readily available substrates. However, there remain challenges in carbonylation reactions where two CO molecules are converted to different groups in the target product. Considering the merit of complex amides, we reported here a copper-catalyzed multi-component borylamidation for the synthesis of γ-boryl amides.

Copper-catalyzed synthesis of β-boryl cyclopropanes 1,2-borocyclopropanation of aryl olefins with CO as the C1 source.

Cyclopropane represents one of the most critical rings and has been found present in various bioactive compounds, especially in clinical medicines. It can be synthesized by the reaction of olefins with diazo-derived carbenoids which are potentially hazardous. Carbonylation is a powerful tool for synthesizing carbonylated or carbon-extended compounds.

Copper-catalyzed defluorinative arylboration of vinylarenes with polyfluoroarenes.

An unprecedented but challenging defluorinative arylboration has been achieved. Enabled by a copper catalyst, an interesting procedure on defluorinative arylboration of styrenes has been established. With polyfluoroarenes as the substrates, this methodology offers flexible and facile access to provide a diverse assortment of products under mild reaction conditions.

Copper-Catalyzed Synthesis of Multideuterium-Labeled Alcohols from Styrenes with CO and D as the Source of the Hydroxymethyl Group.

Deuterated compounds have important applications, especially in the pharmaceutical field. Hence, the development of new and straightforward synthetic methods for the construction of deuterated compounds is becoming more and more attractive. We describe here a copper-catalyzed hydroxymethylation of aryl olefins with CO and D as the source of hydroxymethyl group.

Copper-Catalyzed Boroaminomethylation of Olefins to γ-Boryl Amines with CO as C1 Source.

Boroaminomethylation of olefins is an efficient process to convert hydrocarbons directly into boron-, nitrogen-containing molecules. Such chemicals are a good handle for obtaining more complexed amine derivatives through the various transformations of organoboron. However, using simple and easily available CO as the C1 feedstock to achieve boroaminomethylation is still elusive.

Copper-catalyzed hydroaminocarbonylation of benzylidenecyclopropanes: synthesis of γ,δ-unsaturated amides.

Herein, we have developed a copper-catalyzed hydroaminocarbonylation of benzylidenecyclopropanes under relatively mild conditions. A series of γ,δ-unsaturated amides with a broad range of functional groups were obtained in moderate to good yields. Both dialkyl-substituted and monoalkyl-substituted hydroxylamine derivatives can be applied in this transformation to give the corresponding tertiary and secondary amides successfully.

Copper-catalyzed hydroformylation and hydroxymethylation of styrenes.

Hydroformylation catalyzed by transition metals is one of the most important homogeneously catalyzed reactions in industrial organic chemistry. Millions of tons of aldehydes and related chemicals are produced by this transformation annually. However, most of the applied procedures use rhodium catalysts.

Palladium-Catalyzed Carbonylative Four-Component Synthesis of β-Perfluoroalkyl Amides.

Transition-metal-catalyzed multicomponent carbonylation is one of the most efficient strategies to construct carbonyl-containing compounds. Herein, a palladium-catalyzed four-component perfluoroalkylation/aminocarbonylation of unactivated alkenes with perfluoroalkyl halides, and amines was developed. A wide range of substrates, including anilines, alkylamines, sulfonamides, and hydrazines are all suitable reaction partners for this catalyst system, resulting in various β-perfluoroalkyl amides with good functional-group tolerance and excellent chemoselectivity.

Copper-Catalyzed Alkoxycarbonylation of Alkyl Iodides for the Synthesis of Aliphatic Esters: Hydrogen Makes the Difference.

A copper-catalyzed alkoxycarbonylation transformation of unactivated alkyl iodides has been developed. Various alkyl iodides can be converted into the corresponding -butyl esters in good yields. NaOBu acts as both a nucleophile and a base.

Palladium-Catalyzed Perfluoroalkylative Carbonylation of Unactivated Alkenes: Access to β-Perfluoroalkyl Esters.

Transition-metal-catalyzed multi-component carbonylation represents an efficient strategy for the preparation of various functionalized carbonyl-containing compounds. Herein, we report a general palladium-catalyzed perfluoroalkylative carbonylation of unactivated alkenes using inexpensive and readily available carbon monoxide as the C1 source and perfluoroalkyl halides as the coupling partner. A wide range of phenols and alcohols were transformed into the corresponding β-perfluoroalkyl esters in high yields with broad functional group tolerance and good chemoselectivity.

Palladium-Catalyzed Carbonylative Synthesis of α-Branched Enones from Aryl Iodides and Arylallenes.

In this communication, an interesting carbonylation protocol for the preparation of α-branched enones has been established. Starting from readily available aryl iodides and allenes, with formic acid as the CO source and reductant, moderate to good yields of the desired enones were isolated. Although it is a carbonylation methodology, the use of a CO source can avoid the manipulation of CO gas directly.

Palladium-Catalyzed Oxidative Carbonylative Coupling of Arylallenes, Arylboronic Acids, and Nitroarenes.

In this Letter, a palladium-catalyzed multicomponent procedure for the selective synthesis of α-substituted α,β-unsaturated ketones has been developed. With readily available allenes, arylboronic acids, and nitroarenes as the substrates, the reaction proceeds selectively to the desired α-substituted enones. Notably, no manipulation of carbon monoxide gas is needed here, and Mo(CO) has been applied as a stable solid CO source instead.

Palladium-Catalyzed Amide Synthesis via Aminocarbonylation of Arylboronic Acids with Nitroarenes.

A palladium-catalyzed aminocarbonylation of aryl boronic acids with nitroarenes for the synthesis of amides has been developed. A wide range of substrates were well-tolerated and gave the corresponding amides in moderate to good yields. No external oxidant or reductant was needed in this procedure.

Palladium-Catalyzed Carbonylative Synthesis of α,β-Unsaturated Amides from Styrenes and Nitroarenes.

A procedure on palladium-catalyzed selective aminocarbonylation of styrenes with nitroarenes for the synthesis of α,β-unsaturated amides has been developed. A range of substituted α,β-unsaturated amides were synthesized in moderate to good yields. Interestingly, nitroarenes act as both a nitrogen source and oxidant, and Mo(CO) acts as a solid CO source and reductant in this catalytic system.