Organoselenium-catalyzed enantioselective syn-dichlorination of unbiased alkenes
Organoselenium-catalyzed enantioselective syn-dichlorination of unbiased alkenes
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DOI：
10.1016/j.tet.2019.05.054
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发表时间：
2019-08-02
期刊：
影响因子：
2.1
通讯作者：
Denmark, Scott E.
中科院分区：
文献类型：
--
作者：
Gilbert, Bradley B.;Eey, Stanley T-C;Denmark, Scott E.
烯烃的对映选择性二氯化一直是有机合成中的一个挑战，这是由于亲电氯和亲核氯向烯烃的选择性和独立的前原子递送的局限性。对分离的烯烃进行对映选择性二氯化的一般方法的发展将允许获得各种各样的多卤化天然产物。因此，在亲电有机硒试剂的催化下，烯烃的对映选择性表面二氯化反应已经被开发出来以解决这些限制。本文描述了23种二硒化物作为对映选择性二氯化预催化剂的评价，其最大e.r.为76:24。此外，机理研究表明，一个意想不到的动态动力学不对称转化（DyKAT）过程可能是有效的。(C) 2019 Elsevier Ltd.版权所有。
The enantioselective dichlorination of alkenes is a continuing challenge in organic synthesis owing to the limitations of selective and independent antarafacial delivery of both electrophilic chlorenium and nucleophilic chloride to an olefin. Development of a general method for the enantioselective dichlorination of isolated alkenes would allow access to a wide variety of polyhalogenated natural products. Accordingly, the enantioselective suprafacial dichlorination of alkenes catalyzed by electrophilic organoselenium reagents has been developed to address these limitations. The evaluation of twenty-three diselenides as precatalysts for enantioselective dichlorination is described, with a maximum e.r. of 76:24 Additionally, mechanistic studies suggest an unexpected Dynamic Kinetic Asymmetric Transformation (DyKAT) process may be operative. (C) 2019 Elsevier Ltd. All rights reserved.