C-13 kinetic isotope effects for the addition of lithium dibutylcuprate to cyclohexenone. Reductive elimination is rate-determining
C-13 kinetic isotope effects for the addition of lithium dibutylcuprate to cyclohexenone. Reductive elimination is rate-determining
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DOI：
10.1021/ja9636348
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发表时间：
1997-04-09
影响因子：
15
通讯作者：
Snyder, JP
中科院分区：
文献类型：
--
作者：
Frantz, DE;Singleton, DA;Snyder, JP
二烷基铜酸锂与烯酮的共轭加成是合成有机化学的重要手段。尽管这些反应得到了广泛的应用并付出了大量的努力，但一个清晰的机制图景尚未被描绘出来。House的早期研究提出了一种基于烯酮的还原电位和它们在共轭加成中的反应活性之间的相关性的单电子转移机制。虽然锂烯酮配合物、3电荷转移配合物、4。但后来的研究倾向于把重点放在铜-烯烃π-配合物上
The conjugate addition of lithium dialkylcuprates to enones is a vital tool in synthetic organic chemistry. Despite the broad use of these reactions and abundant effort, a clear mechanistic picture has yet to be delineated. Early studies by House suggested a single-electron-transfer mechanism based on a correlation between the reduction potentials of enones and their reactivity in conjugate additions. 1 Later studies have tended to focus on copper-olefin π-complexes2 as key intermediates, although lithium-enone complexes, 3 charge-transfer complexes, 4