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协同钯和相转移催化实现邻近立体中心Csp3–Csp3键的立体发散构建
作者:小柯机器人 发布时间:2022/11/18 14:51:50

南开大学资伟伟团队通过协同钯和相转移催化实现邻近立体中心Csp3–Csp3键的立体发散构建。相关研究成果发表在2022年11月15日出版的《德国应用化学》。

协同催化已成为形成具有相邻立体中心的Csp3–Csp3键立体发散的最有力工具之一。尽管在这一领域取得了许多成功,但由于竞争的单一催化途径,涉及稳定亲核试剂的立体发散Csp3–Csp3偶联反应仍然具有挑战性。

该文中,研究人员报道了一种协同钯/相转移催化剂体系,该体系能够使1,3-二烯与稳定的亲核试剂氧吲哚进行非对映异构Csp3–Csp3偶联反应。带有季和叔邻位立体中心的顺式和反式偶联产物,都可以以高对映选择性和非对映选择性的高收率选择性生产。在双相体系中通过手性离子对非共价激活稳定的亲核试剂是实现非对映异构的关键因素。

附:英文原文

Title: Stereodivergent Construction of Csp3–Csp3 Bonds Bearing Vicinal Stereocenters by Synergistic Palladium and Phase-Transfer Catalysis

Author: Jingqiang Han, Rixin Liu, Zitong Lin, Weiwei Zi

Issue&Volume: 2022-11-15

Abstract: Synergistic catalysis has emerged as one of the most powerful tools for stereodivergent formation of Csp3–Csp3 bonds bearing vicinal stereocenters. Despite the many successes that have been achieved in this field, stereodivergent Csp3–Csp3 coupling reactions involving stabilized nucleophiles remain challenging because of the competing single-catalysis pathway. Herein, we report a synergistic palladium/phase-transfer catalyst system that enables diastereodivergent Csp3–Csp3 coupling reactions of 1,3-dienes with stabilized nucleophile oxindoles. Both the syn and anti coupling products, bearing quaternary and tertiary vicinal stereocenters, could be selectively produced in good yields with high enantio- and diastereoselectivities. Non-covalent activation of the stabilized nucleophile via chiral ion pair in a biphasic system is a crucial success factor in achieving diastereodivergence.

DOI: 10.1002/anie.202215714

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202215714

期刊信息

Angewandte Chemie:《德国应用化学》,创刊于1887年。隶属于德国化学会,最新IF:12.959
官方网址:https://onlinelibrary.wiley.com/journal/15213773
投稿链接:https://www.editorialmanager.com/anie/default.aspx