Direct Silyl–Heck Reaction of Chlorosilanes

Abstract

A nickel complex/Lewis acid combination effectively catalyzed the direct silyl-Heck reaction of chlorosilanes, which are key raw materials in the organosilicon industry, to give synthetically important alkenylsilane products. Trichlorosilanes, dichlorosilanes, and monochlorosilanes underwent the silyl-Heck reaction to afford the corresponding alkenylsilanes in high yields. In the reactions of dichlorosilanes, a single substitution occurred to give monoalkenylsilanes in a highly selective manner.

Nickel‐Catalyzed Selective Cross‐Coupling of Chlorosilanes with Organoaluminum Reagents

“…Meanwhile, we also reported nickel‐catalyzed silyl‐Heck reaction of chlorosilanes . This research demonstrated 1) the first example of direct catalytic transformation of strong Si−Cl bonds (ca.…”

“…Transition‐metal‐catalyzed cross‐coupling of halosilanes with various coupling partners are attractive methods to synthesize organochlorosilanes with various substituents selectively . Recent research in this field has been conducted by Watson et al ., who reported silyl‐Heck reaction with olefins as well as silyl‐Negishi coupling with organozinc reagents and silyl‐Kumada‐Tamao coupling with Grignard reagents of halosilanes (Scheme c).…”

“…The representative strategies of CÀ Si bond formation [3][4][5][6][7][8][9][10][11] was classified in Scheme 1. Industrially, copper-catalyzed reactions of metal silicon with alkyl chlorides (i. e., the Müller-Rochow "direct process" method), [3] are performed to furnish a mixture of organochlorosilanes (RSiCl 3 , R 2 SiCl 2 , R 3 SiCl, etc.)…”

“…[4,5] Transition-metal-catalyzed cross-coupling of halosilanes with various coupling partners are attractive methods to synthesize organochlorosilanes with various substituents selectively. [6][7][8][9][10][11] Recent research in this field has been conducted by Watson et al, who reported silyl-Heck reaction with olefins [8] as well as silyl-Negishi coupling with organozinc reagents [9] and silyl-Kumada-Tamao coupling with Grignard reagents [10] of halosilanes (Scheme 1c). In these reactions, the scope of the substrates is mainly limited to the use of monohalosilanes (R 3 SiX), and the product selectivity was not discussed in detail.…”

External Electric Field—Phenyl interaction boosts hydrosilylation of substituted alkynes to α‐vinylsilane

“…Vinylsilanes are valuable building blocks in organic synthesis and material chemistry because of their versatile characters, such as low toxicity, high stability, facile manipulations, and a variety of transformations . Accordingly, methods for the preparation of vinylsilanes have gained increased attentions from synthetic chemists, in which the hydrosilylation of alkynes was considered as a simple and straightforward method .…”