Disclosed here is a catalytic strategy for asymmetric access to chiral tetrasubstituted silicon-stereogenic silanes. Our reaction starts with a (covalently) symmetric silane bearing two aldehyde moieties as the substrate. Single-crystal structural analysis shows that the substrate exists as a racemate of two conformational enantiomers because of the presence of a Si/O weak interaction. Mechanistic studies assisted by DFT calculation indicate that the two conformational enantiomers can readily isomerize to each other, and one of the conformational enantiomers of the substrate is favorably activated by a N-heterocyclic carbene catalyst via an overall desymmetrization process to eventually afford optically enriched tetrasubstituted silicon-stereogenic silanes as the products. Our chiral silanes’ products can be readily transformed to a diverse set of silicon stereogenic functional molecules.

Conformational isomerization can be guided by weak interactions such as chalcogen bonding (ChB) interactions. Here we report a catalytic strategy for asymmetric access to chiral sulfoxides by employing conformational isomerization and chalcogen bonding interactions. The reaction involves a sulfoxide bearing two aldehyde moieties as the substrate that, according to structural analysis and DFT calculations, exists as a racemic mixture due to the presence of an intramolecular chalcogen bond. This chalcogen bond formed between aldehyde (oxygen atom) and sulfoxide (sulfur atom), induces a conformational locking effect, thus making the symmetric sulfoxide as a racemate. In the presence of N–heterocyclic carbene (NHC) as catalyst, the aldehyde moiety activated by the chalcogen bond selectively reacts with an alcohol to afford the corresponding chiral sulfoxide products with excellent optical purities. This reaction involves a dynamic kinetic resolution (DKR) process enabled by conformational locking and facile isomerization by chalcogen bonding interactions.