Recent Progress in Asymmetric Synthesis and Application of Difunctionalized Silicon‐Stereogenic Silanes

During the past decades, silicon‐stereogenic compounds have continuously been attracting attention in synthetic chemistry. The preparation of representatives containing reactive silicon–element bonds is thus an interesting task to allow further transformations. Provided that the chiral information can efficiently be transferred in these conversions, reactive silicon‐chiral silanes may lead to interesting new applications. In this microreview we give an overview of difunctionalized silanes containing asymmetrically substituted silicon centers. Several intriguing approaches have been discovered over the years and are presented in terms of their synthetic potential and stereochemical behavior. With a special focus on our recent achievements in the field of silicon‐stereogenic N,O‐silanes, new mechanistic aspects of stereocontrolled nucleophilic substitutions are also discussed, along with innovative coordination capabilities that arise from the unique silicon‐centered asymmetry.