Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023 (China) http://www.asym.dicp.ac.cn; University of the Chinese Academy of Sciences, Beijing 100049 (China).
Angew Chem Int Ed Engl. 2014 Jan 27;53(5):1410-4. doi: 10.1002/anie.201309182. Epub 2013 Dec 18.
The first enantioselective copper-catalyzed decarboxylative propargylic alkylation has been developed. Treatment of propargyl β-ketoesters with a catalyst, prepared in situ from [Cu(CH3 CN)4 BF4 ] and a newly developed chiral tridentate ketimine P,N,N-ligand under mild reaction conditions, generates β-ethynyl ketones in good yields and with high enantioselectivities without requiring the pregeneration of ketone enolates. This new process provides facile access to a range of chiral β-ethynyl ketones in a highly enantioenriched form.
首例手性铜催化脱羧炔丙基烷基化反应已被开发。在温和的反应条件下，用原位生成的[Cu(CH3CN)4BF4]和新开发的手性三齿酮亚胺 P,N,N-配体作为催化剂，处理炔丙基β-酮酯，生成β-乙炔基酮，产率高，对映选择性好，无需预先生成酮烯醇盐。这种新方法为一系列手性β-乙炔基酮提供了一种高对映体过量的简便合成方法。
