Achieving the preparation of enantiomerically enriched S-stereogenic compounds is a long-standing objective in stereoselective synthesis, owing to the fundamental importance and broad applications of these chiral scaffolds in various fields. Despite recent significant advancements, catalyst-controlled stereoselective synthesis of S-stereogenic compounds remains to be a considerable challenge, particularly by means of small-molecule catalysts. Herein, we disclosed an organocatalytic strategy for highly practical and enantioselective sulfinylation of alcohols and amines through the activation of sulfinates by forming mixed sulfinic anhydrides. Tuning the structure of the reactive species with sterically congested moieties, a simple, naturally occurring quinine catalyst effectively controls the chemo- and enantioselectivity over the nucleophilic S–O and S–N bond constructions, affording a wide range of chiral sulfinyl derivatives with excellent optical purities. Notably, the protocol readily facilitates the coupling with various natural products and commercial drugs that could offer an attractive strategy for the late-stage diversification of important biologically intriguing molecules.

由于这些手性支架在各个领域的根本重要性和广泛应用，实现对映体富集的S-立体化合物的制备是立体选择性合成的长期目标。尽管最近取得了重大进展，但催化剂控制的S-立体化合物的立体选择性合成仍然是一个相当大的挑战，特别是通过小分子催化剂。在此，我们公开了一种通过形成混合亚磺酸酐来活化亚磺酸盐来对醇和胺进行高度实用和对映选择性亚磺酰化的有机催化策略。一种简单的天然奎宁催化剂通过空间拥挤部分调节反应物种的结构，有效控制亲核 S-O 和 S-N 键结构的化学和对映选择性，提供各种具有优异光学性质的手性亚磺酰基衍生物纯度。值得注意的是，该协议很容易促进与各种天然产物和商业药物的偶联，这可以为重要的生物学有趣分子的后期多样化提供有吸引力的策略。