Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, P. R. China.
School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai, 200241, P. R. China.
Chemistry. 2019 Dec 2;25(67):15411-15418. doi: 10.1002/chem.201904028. Epub 2019 Nov 6.
A divergent strategy for the facile preparation of various enantioenriched phenylthio-substituted lactones was developed based on Lewis base/Brønsted acid co-catalyzed thiolation of homoallylic acids. The acid-controlled regiodivergent cyclization (6-endo vs. 5-exo) and acid-mediated stereoselective rearrangement of phenylthio-substituted lactones were explored. Experimental and computational studies were performed to clarify the origins of the regioselectivity and enantioselectivity. The calculation results suggest that C-O and C-S bond formation might occur simultaneously, without formation of a commonly supposed catalyst-coordinated thiiranium ion intermediate and the potential π-π stacking between substrate and SPh as an important factor in the enantio-determining step. Finally, this methodology was applied in the rapid syntheses of the bioactive natural products (+)-ricciocarpin A and (R)-dodecan-4-olide.
基于路易斯碱/布朗斯台德酸共催化的高烯丙基酸硫代反应，开发了一种简便制备各种对映体富集的苯硫基取代内酯的发散策略。探索了酸控制的区域发散环化（6-endo 与 5-exo）和酸介导的苯硫基取代内酯的立体选择性重排。进行了实验和计算研究，以阐明区域选择性和对映选择性的起源。计算结果表明，C-O 和 C-S 键的形成可能同时发生，而不需要形成通常假定的催化剂配位硫𬭩离子中间体，以及底物和 SPh 之间的潜在 π-π 堆积作为对映体决定步骤中的重要因素。最后，该方法应用于生物活性天然产物（+）-ricciocarpin A 和（R）-十二烷-4-内酯的快速合成。
