化学
激进的
氢原子萃取
位阻效应
反应性(心理学)
均分解
氢原子
胺气处理
光化学
药物化学
硼烷
硼烷
立体化学
计算化学
催化作用
有机化学
烷基
硼
替代医学
病理
医学
作者
Hai‐Shan Dang,Valérie Diart,Brian P. Roberts,Derek A. Tocher
出处
期刊:Journal of the Chemical Society
日期:1994-01-01
卷期号: (5): 1039-1045
被引量:28
摘要
The molecular structures of optically active quinuclidine–isopinocampheylborane and of the polycyclic amine–borane formed by cyclisation of N-nopylpyrrolidine–borane have been determined by X-ray crystallography. These and related amine–borane complexes have been used previously as polarity-reversal catalysts to bring about kinetic resolution of racemic esters and ketones. The key step in these resolutions is enantioselective H-atom abstraction from an α-C–H group in the carbonyl compound by the chiral amine–boryl radical derived from the catalyst. Ab initio and semi-empirical molecular orbital calculations have been carried out for representative transition states involved in H-atom transfer to amine–boryl radicals and the roles of dipole–dipole interactions, stereoelectronic effects and hydrogen-bonding have been investigated. The steric demands of a variety of amine–boryl radicals in H-atom transfer reactions have been assessed by determining the relative rates of abstraction from the α-C–H bonds in diethyl malonate and diethyl methylmalonate.
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