Sulfilimines are versatile synthetic intermediates and important moieties in bioactive molecules. However, their applications in drug discovery are underexplored, and efficient asymmetric synthetic methods are highly desirable. Here, we report a transition metal–free pentanidium-catalyzed sulfur alkylation of sulfenamides with exclusive chemoselectivity over nitrogen and high enantioselectivity. The reaction conditions were mild, and a wide range of enantioenriched aryl and alkyl sulfilimines were obtained. The synthetic utility and practicability of this robust protocol were further demonstrated through gram-scale reactions and late-stage functionalization of drugs.

中文翻译：

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通过次磺酰胺的有机催化对映选择性硫烷基化合成手性硫酰亚胺


硫胺是多功能的合成中间体，是生物活性分子中的重要部分。然而，它们在药物发现中的应用尚未得到充分探索，高效的不对称合成方法非常可取。在这里，我们报道了次磺酰胺的无过渡金属戊催化的硫烷基化反应，对氮具有独特的化学选择性和高对映选择性。反应条件温和，得到范围很广的对映体富集芳基和烷基硫胺。这种稳健方案的合成效用和实用性通过克级反应和药物的后期功能化进一步证明。