Guan Zhipeng, Zhu Shuxiang, Wang Siyuan, Wang Huamin, Wang Siyuan, Zhong Xingxing, Bu Faxiang, Cong Hengjiang, Lei Aiwen
College of Chemistry and Molecular Sciences and The Institute for Advanced Studies (IAS), Wuhan University, Wuhan, 430072, Hubei, P. R. China.
Angew Chem Int Ed Engl. 2021 Jan 18;60(3):1573-1577. doi: 10.1002/anie.202011329. Epub 2020 Nov 12.
Ethers (C-O/S) are ubiquitously found in a wide array of functional molecules and natural products. Nonetheless, the synthesis of imino sulfide ethers, containing an N(sp )=C(sp )-O/S fragment, still remains a challenge because of its sensitivity to acid. Developed here in is an unprecedented electrochemical oxidative carbon-atom difunctionalization of isocyanides, providing a series of novel multisubstituted imino sulfide ethers. Under metal-free and external oxidant-free conditions, isocyanides react smoothly with simple and readily available mercaptans and alcohols. Importantly, the procedure exhibited high stereoselectivities, excellent functional-group tolerance, and good efficiency on large-scale synthesis, as well as further derivatization of the products.
醚（C-O/S）广泛存在于各种功能分子和天然产物中。然而，由于对酸敏感，含有N(sp )=C(sp )-O/S片段的亚氨基硫醚的合成仍然是一个挑战。本文开发了一种前所未有的异腈电化学氧化碳原子双官能化反应，可提供一系列新型的多取代亚氨基硫醚。在无金属和无外部氧化剂的条件下，异腈能与简单易得的硫醇和醇顺利反应。重要的是，该方法具有高立体选择性、出色的官能团耐受性、大规模合成的良好效率以及产物的进一步衍生化能力。
