Tan Yun-Xuan, Liu Xing-Yu, Zhao Yi-Shuang, Tian Ping, Lin Guo-Qiang
CAS Key Laboratory of Synthetic Chemistry of Natural Substances , Shanghai Institute of Organic Chemistry , University of Chinese Academy of Sciences, 345 Lingling Road , Shanghai 200032 , China.
School of Physical Science and Technology , ShanghaiTech University , 100 Haike Road , Shanghai 201210 , China.
Org Lett. 2019 Jan 4;21(1):5-9. doi: 10.1021/acs.orglett.8b03288. Epub 2018 Nov 9.
An arylation/intramolecular conjugate addition of cyclohexadienone-containing 1,6-enynes has been established through initiation by manganese(I)-catalyzed C-H bond activation. This tandem reaction involved unusual E/ Z-isomerized alkenyl-Mn intermediates and proceeded smoothly with high chemoselectivities and perfect atom economy. The cyclization products could be further transformed to various structures. Mechanistic studies suggested that cleavage of the C-H bond was involved in the turnover-limiting step, and a manganese carbene anion intermediate was proposed to explain such an E/ Z isomerization process.
通过锰（I）催化的C-H键活化引发，已建立了含环己二烯酮的1,6-烯炔的芳基化/分子内共轭加成反应。这种串联反应涉及不寻常的E/Z异构化烯基-锰中间体，并以高化学选择性和完美的原子经济性顺利进行。环化产物可以进一步转化为各种结构。机理研究表明，C-H键的断裂参与了限速步骤，并提出了锰卡宾阴离子中间体来解释这种E/Z异构化过程。
