Silicon‐Stereogenic Monohydrosilane: Synthesis and Applications

Abstract

Optically active organosilanes have been demonstrated to be versatile chiral reagents in synthetic chemistry since the early seminal contributions by Sommer and Corriu. Among these silicon-containing chiral architectures, monohydrosilanes, which bear a SiÀ H bond, hold a unique position because of their facile transformations through stereospecific Si-carbon or Si-heteroatom bond-formation reactions. In addition, those compounds have also been leveraged as chiral reagents for alcohol resolution, chiral auxiliaries, mechanistic probes, as well as potential optoelectronic materials. This Minireview comprehensively summarizes the synthesis and synthetic applications of silicon-stereogenic monohydrosilanes, particularly the advances in the transition-metal-catalyzed asymmetric synthesis of this class of functional molecules.

Organocatalytic DYKAT of Si-Stereogenic Silanes

“…53 The described two-step approach here may facilitate the wide utilization of such hydrosilanes as chiral auxiliaries, protecting groups, reagents, and synthetic precursors. 54 To shed light on the underlying reaction mechanism of the discovered DYKAT, we conducted a time-course study for the reaction of allyl silane 1a with propofol 2 catalyzed by IDPi 3d in toluene at −20 °C for 3 days. The enantiopurity of the remaining silane 1a and product 4a was continuously monitored during the course of the reaction (Figure 1A).…”

Enantioselective Construction of Si-Stereogenic Linear Alkenylhy-drosilanes via Copper-Catalyzed Anti-Markovnikov Hydrosilyla-tion of Alkynes

“…[9][10][11][12][13][14][15][16] During recent decades, impressively, transition metal-catalyzed desymmetrization of dihydrosilanes and tetraoganosilanes have provided an alternative access to construct the silicon-stereogenic center. [17][18][19][20][21] In fact, the asymmetric catalytic transformation of dihydrosilanes has attracted considerable attention because the obtained chiral product retains a reactive Si-H bond may offer more possibilities for further functionalization. The popular methods of intermolecular desymmetrization of dihydrosilanes to generate silicon-stereogenic silanes include: 1) hydrosilylation of alkenes [27][28][29] , 1,3-dienes 30 , alkynes [31][32][33] and ketones [34][35][36] ; 2) carbenes insertion [37][38][39] ; 3) arylation and dehydrogenative coupling reactions [40][41][42][43][44] ; 4) alcoholysis [45][46][47][48][49][50][51][52][53][54] etc (Scheme 1a).…”