Copper-Catalyzed Anti-Markovnikov Hydrosilylation of Terminal Alkynes

Abstract

A copper-catalyzed anti-Markovnikov hydrosilylation of alkynes with PhSiH 3 was reported. This reaction represents a notable and efficient example on copper-catalyzed hydrosilylatioin of alkynes, which shows excellent recognition between the terminal and internal triple bonds. Various (hetero)aromatic and aliphatic substituted terminal alkynes underwent this reaction to afford the (E)-vinylsilanes in high yields and with excellent regioselectivity.

Cyclic vs. acyclic alkyne towards Hg2+ ion detection: combined experimental and theoretical studies

“…There are some reactions where both the terminal and internal alkynes participate similarly, [43][44][45][46] while there are others that are specific only for terminal alkynes such as reaction with a base or alkyne-alkyne coupling reactions. [47][48][49] However, to unambiguously compare the differences in reactivity between terminal and internally conjugated alkynes, their basic molecular platform must be same, only varying the alkyne positions. Consequently, any factor other than the alkyne positions do not play a role in their difference.…”

Transition-Metal-Catalyzed Stereo- and Regioselective Hydrosilylation of Unsymmetrical Alkynes

“…(Table 2, entries 13-15). [70][71][72] It must be noted that most of the above mentioned non-noble metal catalyzed system successfully achieved selective addition reactions of mono-or disubstituted hydrosilanes to alkynes. This is very rare among noble metal catalysts, as noble metal catalyzed reactions often have difficulty in curbing further secondary hydrosilylation of alkenyl silicon products with alkynes.…”

“…In addition, catalysts based on Ti, Sc and Cu were also reported to achieve -E-selective alkyne hydrosilylation (entries 13-15). [70][71][72] This document was downloaded for personal use only. Unauthorized distribution is strictly prohibited.…”

“…In addition, catalysts based on Ti, Sc and Cu were also reported to achieve -E-selective alkyne hydrosilylation (entries 13-15). [70][71][72]…”

Synthesis of Structurally Diverse Allylsilanes via Copper-Catalyzed Regiodivergent Hydrosilylation of 1,3-Dienes

“…Based on the precedent of metal-catalyzed hydrosilylation of 1,3-dienes , and previous reports on copper-catalyzed hydrosilylation of unsaturated bonds, a plausible mechanism for the regiodivergent hydrosilylation is proposed in Scheme Initially, the reaction of copper salt and silane generates the Cu–H species. Then coordination of Cu–H species with 1,3-dienes formed the intermediate ( I ).…”