马尔科夫尼科夫法则
催化作用
环氧化物
化学
戒指(化学)
铬
组合化学
氢
氢原子
钛
选择性
有机化学
药物化学
区域选择性
烷基
作者
Chengbo Yao,Tobias Dahmen,Andreas Gansäuer,Jack R. Norton
出处
期刊:Science
[American Association for the Advancement of Science (AAAS)]
日期:2019-05-24
卷期号:364 (6442): 764-767
被引量:128
标识
DOI:10.1126/science.aaw3913
摘要
Markovnikov falls to chromium and titanium Ring opening of strained triangular epoxides is a versatile method for making alcohols. However, these reactions are limited by their tendency to leave the oxygen on the more heavily substituted carbon, in accord with the Markovnikov rule. Yao et al. now show that a pair of catalysts working cooperatively can invert this selectivity pattern. A titanium catalyst pries the ring open while a chromium catalyst activates and delivers hydrogen. In an unusual mechanistic twist, the chromium complex appears to deliver a hydrogen atom, a proton, and an electron at different stages of the cycle. Science , this issue p. 764
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