Transition-metal-catalyzed enantioselective C−H silylation

Abstract

Organosilanes are important and valuable compounds that have found widespread applications in the fields of organic chemistry, agrochemistry, medicinal chemistry, and materials science. In modern synthetic chemistry, molecules featuring carbon−silicon bonds have attracted considerable interest given that these motifs can be efficiently converted to a wide range of functionalities. Among various approaches, transition-metal-catalyzed C−H silylation has emerged as a powerful tool for the synthesis of silicon-containing functional molecules, which has profoundly accelerated the iteration of organosilicon science. Despite the rapid development of C−H silylation, the enantioselective version of this elegant methodology was not known until 2013. In this review, we aim to summarize recent advances in the area of enantioselective C−H silylation mediated by chiral transition-metal catalysts, organized by the different forms of chirality of the enantioenriched organosilanes. We highlight the great potential of this methodology and intend to inspire further research and applications in this emerging area. Transition-metal-catalyzed enantioselective C–H silylation is one of the most effective ways to access silicon-containing chiral molecules, which have great utility in areas ranging from synthetic chemistry and medicinal chemistry to materials science. The purpose of this review is to provide a general overview of the asymmetric synthesis of organosilanes featuring different forms of chirality via transition-metal-catalyzed enantioselective C−H silylation. The uniqueness of this review is a particular focus on the diverse scaffolds of enantioenriched silanes that arose by different forms of chirality and an emphasis on the recently emerged Si-CADC strategy toward silicon-stereogenic silanes. We hope that this review will shed light on new perspectives and provide guidance for chemists who are interested in this burgeoning research area. Chiral organosilanes are important and valuable compounds that have found widespread applications in the field of synthetic chemistry, medicinal chemistry, and materials science. Over the past decade, transition-metal-catalyzed enantioselective C–H silylation has gradually maturated into a powerful tool for the synthesis of these silicon-containing molecules, featuring axial, helical, planar, carbon-stereogenic, or silicon-stereogenic chiralities, which has profoundly accelerated the iteration of chiral organosilicon science.