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手性环金属化恶唑啉金(III)配合物催化的炔烃不对称碳羧化反应。

Chiral Cyclometalated Oxazoline Gold(III) Complex-Catalyzed Asymmetric Carboalkoxylation of Alkynes.

机构信息

State Key Laboratory of Chemical Biology and Drug Discovery, Department of Applied Biology and Chemical Technology , The Hong Kong Polytechnic University , Hung Hom , Hong Kong.

Department of Chemistry , Southern University of Science and Technology , Shenzhen 518055 , People's Republic of China.

出版信息

Org Lett. 2019 Aug 16;21(16):6289-6294. doi: 10.1021/acs.orglett.9b02171. Epub 2019 Aug 6.

Abstract

Asymmetric catalysis by using novel chiral O,O'-chelated 4,4'-biphenol cyclometalated oxazoline gold(III) complexes has been developed. A high yield (≤89%) and a high enantioselectivity (≤90% ee) were achieved in asymmetric carboalkoxylation of alkynes. Enantioselectivity could be significantly improved from 19% to 90% ee by increasing the steric size of the substituent on the chiral oxazoline ligand. Catalytically active Au species and the origin of chiral induction are proposed.

摘要

新型手性 O,O'-螯合 4,4'-联苯酚环金属化恶唑啉金(III)配合物的不对称催化已被开发。在炔烃的不对称碳羧化反应中,取得了高产率(≤89%)和高对映选择性(≤90%ee)。通过增加手性恶唑啉配体上取代基的空间位阻,对映选择性可从 19%显著提高至 90%ee。提出了催化活性的 Au 物种和手性诱导的起源。

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