Discovery and synthesis of atropisomerically chiral acyl-substituted stable vinyl sulfoxonium ylides.

Atropisomerism is a type of conformational chirality that plays a critical role in various fields of chemistry, including synthetic, medicinal and material chemistry, and its impact has been widely recognized. Although chiral atropisomerism in rotationally restricted aryl-aryl bonds has garnered substantial interest and led to important discoveries in chiral catalysts and drug development, the exploration of non-aryl atropisomers has fallen behind. Here we reveal a previously unexplored form of non-aryl atropisomerism by linking a sterically congested olefin to a sulfoxonium ylide. A streamlined synthetic approach to these novel molecules was developed through the hydrofunctionalization of alkynyl sulfoxonium ylides. Notably, an enantioselective organocatalytic strategy was developed to prepare these non-aryl atropisomers in high optical purity. This form of atropisomerism offers new routes for investigating the functional properties of axially chiral molecules.