State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University, Guiyang, 550025, China.
Division of Chemistry & Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, Singapore, 637371, Singapore.
Nat Commun. 2022 Aug 15;13(1):4793. doi: 10.1038/s41467-022-32428-4.
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（如硫属键合（ChB）相互作用）来引导。在这里，我们报告了一种通过构象异构化和硫属键合相互作用来实现手性亚砜不对称合成的催化策略。该反应涉及作为底物的带有两个醛基部分的亚砜，根据结构分析和 DFT 计算，由于存在分子内硫属键，该亚砜以外消旋混合物的形式存在。这种在醛（氧原子）和亚砜（硫原子）之间形成的硫属键诱导构象锁定效应，从而使对称亚砜成为外消旋体。在 N-杂环卡宾（NHC）作为催化剂的存在下，硫属键活化的醛基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。该反应涉及通过构象锁定和硫属键合相互作用的易位来实现动态动力学拆分（DKR）过程。
