Silylative coupling of olefins with vinylsilanes in the synthesis of functionalized alkenes

Abstract

The development of highly selective methods for the synthesis of functionalized olefins, based on sequential catalytic reactions of organometallic reagents, has been the subject of extensive study because of their versatile applications in organic synthesis and materials science. The silylative coupling of olefins with vinyl-substituted organosilicon compounds (discovered in our group) represents one of the most efficient and straightforward methods for the synthesis of stereodefined alkenylsilanes and bis (silyl) alkenes, which are particularly attractive scaffolds for further transformations including palladium-catalyzed cross-coupling with organic halides (Hiyama coupling) or electrophile-induced desilylation. The article highlights the recent developments and covers the literature mainly from the last decade in the sequential (also one-pot) synthetic strategies including ruthenium-catalyzed silylative coupling followed by desilylative cross-coupling, acylation and halogenation, leading to stereodefined organic derivatives such as (E)-alkenyl halides, (E)-α,β-unsaturated ketones or arylene-(E)-vinylene derivatives which are widely applied as fine chemicals, functional materials or building blocks in organic synthesis. † Dedicated to Prof. Ei-ichi Negishi on the occasion of his 80th birthday.

Catalytic Formation of Silicon–Heteroatom (N, P, O, S) Bonds

“…described an innovative method for the ruthenium‐catalyzed dealkenative N‐silylation of amines by substituted vinylsilanes . Various aromatic and aliphatic amines react with substituted vinylsilanes, which act as silylating agents and hydrogen acceptors to form the corresponding silylamines with the elimination of olefin molecules (Scheme ).…”

Study on the mechanism of catalytic synthesis of dimethyldichlorosilane by AlCl3/MIL‐53(Al)@γ‐Al2O3

“…[7,8] How to transform and recycle the by-products in the synthesis of dimethyldichlorosilane is the current research direction of researchers. The disproportionated synthesis method of organosilicons (i.e., the redistribution method) that has been extensively studied over the past decades, [9][10][11] it can well solve the problem of the utilization of trimethylchlorosilane and methyltrichlorosilane and provides new insights for the synthesis of compounds such as dimethyldichlorosilane. As a classical strong Lewis acid catalyst, AlCl 3 shows good catalytic activity in the disproportionation of methyltrichlorosilane and trimethylchlorosilane to dimethyldichlorosilane.…”

A highly efficient synthesis of 1-trimethylsilyl-2-arylcyclopentenes using two consecutive stages of aqueous and anhydrous reactions

“…The strategy has been used in the synthesis of complex organic molecules. 2 Simultaneously, cross coupling reactions involving C-C bond formations are employed in the synthesis of wide array of organic molecules. [3][4][5][6][7] Among the many reactions, the Suzuki cross-coupling reaction of aryl/vinyl halides or triflates with boronic acids has gained importance for the synthesis of novel aryl/vinyl molecules.…”