化学
对映选择合成
催化作用
区域选择性
结合
组合化学
共轭体系
卤化物
铜
三键
转移加氢
有机化学
双键
钌
数学分析
聚合物
数学
作者
Guosheng Wu,Yuan Yao,Gen Li,Xue Zhang,Hui Qian,Shengming Ma
标识
DOI:10.1002/anie.202112427
摘要
Naturally occurring conjugated allenynes are of general interest owing to their potent and various biological activities. The 1,5-H transfer of alka-1,4-diyn-3-yl amines would be one of the most straightforward yet challenging approaches to such compounds since, in principle, two regioisomers may be formed involving two C-C triple bonds. Herein, a catalytic recipe of copper halides with mixed oxidation states, i.e., CuCl/CuBr2 , has been identified to address the issues of the side reaction of conjugate addition and the selectivity of 1,5-H transfer of alka-1,4-diyn-3-yl amines in EATA (enantioselective allenation of terminal alkynes) reaction involving 2-alkynals. This method provided various allenynes with excellent enantioselectivities, and was also applied to the first highly enantioselective total synthesis of natural product scorodonin. Mechanistic studies and DFT calculations elucidated the regioselectivity for the observed 1,5-H transfer.
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