期刊
ACS CATALYSIS
卷 10, 期 12, 页码 6682-6690出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.0c00220
关键词
gold(I) catalysis; gold(III) catalysis; cycloaddition; enynal/enynone; reaction intermediates
资金
- National Natural Science Foundation of China [21671066]
Metal bound isobenzopyrylium species are proposed as reactive intermediates in transition-metal-catalyzed [3 + 2] or [4 + 2] cyclizations of o-alkynylbenzaldehydes (enynals) or o-alkynylarylketones (enynones). Because of their high reactivity, isolation and structural characterization of such intermediates have remained elusive. Herein, we report the isolation of such gold(I)and gold(III)-bound isobenzopyrylium intermediates, and two of them have been characterized by X-ray diffraction analysis. When reacting with reaction partners, such as styrene and phenyl acetylene, the Au(I) intermediate exhibited a reaction rate much faster than that of the Au(III) species. A degradation pathway of active Au(III)-carbene intermediate was observed, leading to release of Au(I) species and consequent formation of a dichloride compound. In other related catalytic reactions, the Au(I) intermediate could react well with a range of cyclization partners, whereas the Au(III) intermediate did not work. The above observations indicate that Au(I) species is probably the real catalyst in such gold-catalyzed transformations of o-alkynylbenzaldehydes and o-alkynylarylketones.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据