B(C₆F₅)₃-Catalyzed C–Si/Si–H Cross-Metathesis of Hydrosilanes

Abstract

The substituent redistribution of hydrosilanes on silicon through C-Si and Si-H bond cleavage and reformation is of great interest and importance, but this transformation is usually difficult to achieve in a selective fashion. By using electron-rich aromatic hydrosilanes, we have achieved for the first time the selective C-Si/Si-H bond homo- and cross-metathesis of a series of hydrosilanes in the presence of a boron catalyst B(CF). This protocol features simple reaction conditions, high chemoselectivity, wide substrate scope, and high functionality tolerance, offering a new pathway for the synthesis of multisubstituted functional silanes.

Synthesis of substituted quinolines via B(C6F5)3‐catalyzed aniline‐aldehyde‐pyruvate oxidative annulation

“…Based on our findings and the related references, a plausible reaction mechanism for the present B(C 6 F 5 ) 3 ‐catalyzed aniline‐aldehyde‐pyruvate annulation reaction is depicted in Scheme . Upon heating, B(C 6 F 5 ) 3 is generated from a Lewis adduct or the hydroxy borate to activate the imine I derived from aniline 1a and aldehyde 2a , which then undergoes nucleophilic…”

“…B(C 6 F 5 ) 3 , reported in 1964, re‐emerged as a paradigm for small molecule activation in the past decade, especially as a component in frustrated Lewis pairs (FLPs) chemistry . Moreover, B(C 6 F 5 ) 3 has been successfully employed in various other transformations . One of the research hotspots is the borane‐catalyzed multicomponent reactions (MCRs).…”

New Control Over Silicone Synthesis using SiH Chemistry: The Piers–Rubinsztajn Reaction

“…In as eries of seminal papers Chojnowski and co-workers demonstrated that exchange of H/O ligands at silicon can occur in the presence of B(C 6 F 5 ) 3 ; [22] ap rocess that has recently been exploited to create new arylsilanes. [24] The consequences of this are twofold:f irst, chain extension can arise with concomitantr elease of the reactive, volatile, Me 2 SiH 2 and, second, redistribution of internal SiH compounds can lead to the formation of new SiH groups on the polymer backbone ( Figure 5). [22b, 25] The PR reaction is avery efficient process for the preparation of simple methyl-and phenylsilicones.…”

Catalytic Isofunctional Reactions—Expanding the Repertoire of Shuttle and Metathesis Reactions

“…[153] This reaction was found to be efficiently catalyzed by the Lewis acidic B(C 6 F 5 ) 3 ,w hich has recently proved to be proficient in the activation of SiÀH bonds. [153] This reaction was found to be efficiently catalyzed by the Lewis acidic B(C 6 F 5 ) 3 ,w hich has recently proved to be proficient in the activation of SiÀH bonds.…”