Stereoselective Synthesis of Cis- and Trans-Tetrasubstituted Vinyl Silanes Using a Silyl-Heck Strategy and Hiyama Conditions for Their Cross-Coupling

Abstract

We report a palladium-catalyzed, three-component carbosilylation reaction of internal symmetrical alkynes, silicon electrophiles, and primary alkyl zinc iodides. Depending on the choice of ligand, stereoselective synthesis of either cis- or trans-tetrasubstituted vinyl silanes is possible. We also demonstrate conditions for the Hiyama cross-coupling of these products to prepare geometrically defined tetrasubstituted alkenes.

Development of a Radical Silylzincation of (Het)Aryl‐Substituted Alkynes and Computational Insights into the Origin of the trans‐Stereoselectivity

“…As part of this work, we have also demonstrated that this trans ‐silylzincation reaction is not fundamentally restricted to terminal alkynes. Even though further research is still necessary to obtain satisfactory procedures for synthetic purposes, this approach could offer a valuable solution for the stereodefined preparation of tetrasubstituted vinylsilanes, which remains an unsolved problem [31] …”

Regioselective anti-Silyllithiation of Propargylic Alcohols

“…The known syntheses of such tetrasubstituted silylalkenes generally operate through syn-functionalization. [27][28][29][30][31] Thus, anti-carbosilylation across an internal carbon-carbon triple bond has been a daunting challenge that has been answered only in the recent three reports (Scheme 1B). Riant answered to this issue by the conjugate addition of silylcopper species followed by trapping with an allylic cation.…”

“…Riant answered to this issue by the conjugate addition of silylcopper species followed by trapping with an allylic cation. 28 In the iron-catalyzed reaction by Nakamura 30 and the palladium-catalyzed reaction by Watson, 31 formal anti-carbosilylations have been devised as a solution mostly for the symmetric internal alkynes. Accordingly, to address the issues associated with the intrinsic One of the most well-known transformations that facilitate antiaddition to a triple bond is the reaction of coordinating nucleophilic species such as Grignard reagents or organolithiums to non-terminal propargylic alcohols.…”

Theoretical investigation on the effect of the ligand on bis-silylation of C(sp)–C(sp) by Ni complexes

“…Although many production methods can be used to construct vinylsilane, the synthesis of tetra-substituted vinylsilane remains challenging for researchers. [17][18][19][20][21][22][23] Based on the above-mentioned experimental research results, the author focussed on the following contents. Introducing the directing group in silane, which can be coordinated with metal centre Ni, can improve the catalytic activity of Ni.…”