苄基官能化是将容易获得的芳烃原料转化为更有用的分子的便捷方法。然而,由苄基卤化物或类似前体形成碳阴离子苄基物种远非微不足道。另一种方法是苯乙烯与合适的偶联伙伴直接反应,但这些反应通常涉及使用贵金属过渡金属催化剂。在此,我们报告了从苯乙烯中轻松方便地生成活性苄基阴离子物质。通过使用庞大的频哪醇硼烷源对苯乙烯双键进行Cu I催化的 Markovnikov 硼氢化,然后用 KO t Bu 处理以促进 C 的空间诱导裂解B键产生苄型碳负离子。用各种亲电子试剂(包括 CO 2、CS 2、异氰酸酯和异硫氰酸酯)淬灭该中间体,可促进在苄基碳原子上形成C C 键。这种方法的实用性在非甾体抗炎药 (±)-氟比洛芬的三步两锅合成中得到了证明。
Photoextrusion of sulfur dioxide from aryl methyl sulfones: exploration of the mechanism by chemical trapping, chiral and CIDNP probes. 27
作者:Richard S. Givens、Borys Hrinczenko、Jerry H. S. Liu、Bogdan Matuszewski、Joan Tholen-Collison
DOI:10.1021/ja00318a037
日期:1984.3
Rendements quantiques de disparition de SO 2 pour les sulfones indiques. Constantes de vitesse de fluorescence. Mecanismes
Rendements quantiques de disparition de SO 2 pour les sulfones indiques。Constantes de vitesse de 荧光。机制
Mechanistic studies of the photodecomposition of arylmethyl sulfones in homogeneous and micellar solutions
作者:Ian R. Gould、Chen Ho Tung、Nicholas J. Turro
DOI:10.1021/ja00318a038
日期:1984.3
The mechanism of photodecomposition of aryl sulfones has been investigated by using both steady-state and time-resolved techniques. Direct evidence for radical and triplet-state intermediates is provided. A correlation is found between the dynamics of reaction of the intermediate triplet states with the stabilities of the intermediate radicals.