苏黎世联邦理工学院Bill Morandi课题组取得一项新突破。他们研究出以酸氯化物为一氧化碳和碳源，钯催化炔烃的碳甲酰化反应。 该研究于2021年1月29日发表于国际一流学术期刊《自然—化学》。

研究人员表示，氢甲酰化是在不饱和底物上同时安装碳氢键和醛基的反应，是工业和学术界最重要的催化反应之一。考虑到创造新的C-C键在合成上的重要性，以形成新的C-C键代替C-H键的碳甲酰化反应的发展，将具有巨大的合成潜力，可迅速增加有价值的醛类化合物的分子复杂性。然而，利用外源CO原料，四组分合成反应中固有的苛刻的复杂性使直接碳甲酰化反应的开发成为一个巨大的挑战。

该课题组研究人员描述了一种钯催化的策略，该策略以随时可用的芳酰氯为亲电碳和CO原料，并与空间拥挤的氢化硅烷串联，以进行炔烃的立体选择性碳甲酰化反应。该实验设计可以拓展到四种化学发散的羰基化，进一步强调了该策略在羰基化化学中提供的创造性机会。

附：英文原文

Title: Palladium-catalysed carboformylation of alkynes using acid chlorides as a dual carbon monoxide and carbon source

Author: Yong Ho Lee, Elliott H. Denton, Bill Morandi

Issue&Volume: 2021-01-29

Abstract: Hydroformylation, a reaction that installs both a C–H bond and an aldehyde group across an unsaturated substrate, is one of the most important catalytic reactions in both industry and academia. Given the synthetic importance of creating new C–C bonds, the development of carboformylation reactions, wherein a new C–C bond is formed instead of a C–H bond, would bear enormous synthetic potential to rapidly increase molecular complexity in the synthesis of valuable aldehydes. However, the demanding complexity inherent in a four-component reaction, utilizing an exogenous CO source, has made the development of a direct carboformylation reaction a formidable challenge. Here, we describe a palladium-catalysed strategy that uses readily available aroyl chlorides as a carbon electrophile and CO source, in tandem with a sterically congested hydrosilane, to perform a stereoselective carboformylation of alkynes. An extension of this protocol to four chemodivergent carbonylations further highlights the creative opportunity offered by this strategy in carbonylation chemistry.

DOI: 10.1038/s41557-020-00621-x

Source: https://www.nature.com/articles/s41557-020-00621-x