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The construction of silicon‐stereogenic silanols via Pd‐catalyzed intermolecular C−H alkenylation with the assistance of a commercially available L‐pyroglutamic acid has been realized for the first time. Employing oxime ether as the directing group, silicon‐stereogenic silanol derivatives could be readily prepared with excellent enantioselectivities, featuring a broad substrate scope and good functional group tolerance. Moreover, parallel kinetic resolution with unsymmetric substrates further highlighted the generality of this protocol. Mechanistic studies indicate that L‐pyroglutamic acid could stabilize the Pd catalyst and provide excellent chiral induction. Preliminary computational studies unveil the origin of the enantioselectivity in the C−H bond activation step. [ABSTRACT FROM AUTHOR]

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 Si−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. [ABSTRACT FROM AUTHOR]

Enantiopure monohydrosilanes are versatile chiral reagents for alcohol resolution and mechanistic investigation. Herein, we have demonstrated the asymmetric synthesis of monohydrosilanes via an intramolecular hydrosilylation strategy. This protocol is suitable for the synthesis of five‐ and six‐membered cyclic monohydrosilanes, including a class of chiral oxasilacycles, with excellent diastereo‐, regio‐, and enantioselectivities. Notably, the catalyst loading could be reduced to 0.1 mol % which makes this one of the most efficient methods to access chiral monohydrosilanes. Mechanistic studies and DFT calculations indicate this Rh‐catalyzed intramolecular asymmetric hydrosilylation reaction might proceed via a Chalk–Harrod mechanism, and the enantio‐determining step was predicted to be oxidative addition of Si−H bond. [ABSTRACT FROM AUTHOR]

The asymmetric synthesis of Si‐stereogenic silanes has attracted great attention due to the increasing values of Si‐containing functional molecules in synthetic chemistry, medicinal chemistry, and material chemistry. Merging organosilicon chemistry with transition‐metal‐catalyzed C−H approach has led to rich sets of new reactions holding great synthetic values. This Minireview aims to summarize the advances in the construction of Si‐stereogenic silanes through the transition‐metal‐catalyzed C−H activation approach. [ABSTRACT FROM AUTHOR]