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铂催化的异恶唑与杂取代炔烃的高区域选择性[5+2]和[4+2]环加成反应:快速构建功能化的 1,3-噁嗪和 2,5-二氢吡啶。

Highly Site Selective Formal [5+2] and [4+2] Annulations of Isoxazoles with Heterosubstituted Alkynes by Platinum Catalysis: Rapid Access to Functionalized 1,3-Oxazepines and 2,5-Dihydropyridines.

机构信息

Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.

State Key Laboratory of Organometallic Chemistry, Shanghai, Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, China.

出版信息

Angew Chem Int Ed Engl. 2017 Jan 9;56(2):605-609. doi: 10.1002/anie.201610042. Epub 2016 Dec 9.

Abstract

Platinum-catalyzed formal [5+2] and [4+2] annulations of isoxazoles with heterosubstituted alkynes enabled the atom-economical synthesis of valuable 1,3-oxazepines and 2,5-dihydropyridines, respectively. Importantly, this Pt catalysis not only led to unique reactivity dramatically divergent from that observed under Au catalysis, but also proceeded via unprecedented α-imino platinum carbene intermediates.

摘要

铂催化异恶唑与杂取代炔烃的[5+2]和[4+2]环加成反应分别实现了有价值的 1,3-恶嗪和 2,5-二氢吡啶的原子经济性合成。重要的是,该铂催化不仅导致了与金催化观察到的显著不同的独特反应性,而且还通过前所未有的α-亚氨基铂卡宾中间体进行。

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