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.

构象异构化可以通过弱相互作用（例如硫族键合（ChB）相互作用）来引导。在这里，我们报告了一种通过利用构象异构化和硫族键合相互作用来不对称获得手性亚砜的催化策略。该反应涉及带有两个醛部分的亚砜作为底物，根据结构分析和DFT计算，由于分子内硫属键的存在，该亚砜以外消旋混合物的形式存在。醛（氧原子）和亚砜（硫原子）之间形成的硫族键引起构象锁定效应，从而使对称亚砜成为外消旋体。在N-杂环卡宾（NHC）作为催化剂存在下，被硫族键激活的醛部分选择性地与醇反应，得到具有优异光学纯度的相应手性亚砜产物。该反应涉及动态动力学拆分 (DKR) 过程，该过程通过硫族键合相互作用实现构象锁定和轻松异构化。