Synergistic Ni/Cu catalyzed migratory arylsilylation of terminal olefins

Synthesis of organosilanes from alkenes is a very important topic owing to their wide applications. A Ni/Cu dual metal-catalyzed arylsilylation of terminal alkenes, featuring migratory selectivity, has been developed. A wide diversity of aliphatic silanes have been prepared from terminal alkenes, aryl halides and Suginome's reagent. This protocol is highlighted by excellent regioselectivity, mild reaction condi-tions and good functional group tolerance. In addition to benzylic positions, carbon-carbon bonds can also be constructed at allylic positions. Preliminary mechanistic studies suggest that the copper cocata-lyst promotes the transmetalation of Suginome's reagent, and the addition of a PyrOx ligand inhibits the formation of side-products from the carbon-Heck pathway. Moreover, studies toward the nature of the PyrOx ligand revealed that the steric hindrance of the oxazoline moiety greatly affects the chain-walking process, but not the arylation step. (c) 2020 Science China Press. Published by Elsevier B.V. and Science China Press. All rights reserved.

Automated summary

This article describes a Ni/Cu dual metal-catalyzed arylsilylation reaction for the synthesis of various aliphatic silanes from terminal alkenes, aryl halides and Suginome's reagent. The reaction exhibits excellent regioselectivity, mild conditions and good functional group tolerance, with the added presence of a PyrOx ligand inhibiting side-product formation. Further mechanistic studies suggest the significance of the copper cocatalyst in promoting transmetalation of Suginome's reagent.