Nickel‐Catalyzed Decarboxylative C–Si Bond Formation: A Regioselective Cross‐Coupling Between Trialkyl Silanes and α,β‐Unsaturated Carboxylic Acids

Abstract

This report presents the first example of nickel-catalyzed mild decarboxylative cross-coupling reaction for the regioselective formation of C-Si bond. An easily accessible and significantly stable Ni (dmg) 2 owes the role of key promoter. This reaction is highly functional group tolerant and offers α,β-unsaturated silanes in synthetically useful yields. The reaction gives access to the successful utilization of otherwise difficult trialkyl silanes as coupling partners and operates at a moderate temperature, which is beneficial to deal with highly volatile silanes.

Nickel‐Catalysed Decarboxylative Coupling Reactions – An Overview

“…A regioselective C−Si bond construction through Ni‐catalysed decarboxylative cross‐coupling was developed for the first time in 2019 [69] . The cross‐coupling of trialkyl silanes 155 with α,β‐unsaturated carboxylic acids (( E )‐cinnamic acids 124 or alkynoic acids 96 ) was carried out under the optimized conditions of 20 mol % of Ni(dmg) 2 and 3 equivalents of tert ‐butyl hydroperoxide (TBHP) at 60 °C for 12 h to provide a range of trialkyl (alkenyl/alkynyl)silanes 156 or 157 (Scheme 51).…”

Recent advances in catalytic decarboxylative transformations of carboxylic acid groups attached to a non-aromatic sp2or sp carbon

“…69 In a report, Kandasamy and co-workers presented a nickel catalysed decarboxylative transformation of phenylpropiolic acid (172a) with trialkyl silanes 175 towards the formation of alkynyl silanes 176 (Scheme 56). 70 The catalyst system, comprising of Ni(dmg) 2 complex and tert-butylhydrogen peroxide, facilitates the addition of a silyl radical to the alkynoic acid, which subsequently undergoes decarboxylation to yield alkynylsilanes 176 as the product.…”