Tan Pengwei, Wang Haoran, Wang Sunewang R
Chang-Kung Chuang Institute, School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Lu, Shanghai 200241, China.
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, East China Normal University, 3663 North Zhongshan Lu, Shanghai 200062, China.
Org Lett. 2021 Apr 2;23(7):2590-2594. doi: 10.1021/acs.orglett.1c00498. Epub 2021 Mar 23.
An unprecedented reductive [2 + 1] annulation of α-keto esters with alkynones mediated by P(NMe) is described. Although this nonmetal cyclopropenation is a nucleophilic process, attributed to the ester migration via a formal [2 + 2] cycloaddition reaction of Kukhtin-Ramirez adducts and alkynones followed by a fragmentation, cyclopropenes with an unbiased alkene scaffold are formed in good to excellent yields, thus providing a promising complementarity to electrophilic metal-catalyzed cyclopropenation.
本文描述了一种由P(NMe)介导的α-酮酯与炔酮前所未有的还原[2 + 1]环化反应。尽管这种非金属环丙烷化是一个亲核过程，归因于通过Kukhtin-Ramirez加合物与炔酮的形式[2 + 2]环加成反应进行酯迁移，随后发生碎片化，但具有无偏向烯烃骨架的环丙烯以良好至优异的产率形成，从而为亲电金属催化的环丙烷化提供了有前景的互补方法。
