Investigation of the transition-metal- and acid-catalyzed reactions of β-(N-tosyl)amino diazo carbonyl compounds
Investigation of the transition-metal- and acid-catalyzed reactions of β-(N-tosyl)amino diazo carbonyl compounds
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DOI：
10.1021/jo0259818
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发表时间：
2003-02-07
影响因子：
3.6
通讯作者：
Wang, JB
中科院分区：
文献类型：
--
作者：
Jiang, N;Ma, ZH;Wang, JB
通过N-对甲苯磺酰亚胺与酰基重氮甲烷的亲核缩合反应，合成了一系列β-(N-对甲苯磺基)氨基重氮羰基化合物。研究了这些重氮羰基化合物在不同催化条件下的重氮分解，包括Rh(II)羧酸盐、铜(I)和铜(II)络合物、PhCO2Ag/Et3N、TsOH和SnCl2.2H(2)O。结果表明，在以PhCO2Ag/Et3N为催化体系时，大多数情况下重氮分解优先生成1，2-芳基迁移产物，但1，2-氢化物迁移占主导地位。用Hammett关联分析了1，2-芳基迁移的电子效应。讨论了控制迁徙偏好的因素和反应的机制方面。
A series of beta-(N-tosyl)amino diazo carbonyl compounds have been prepared by nucleophilic condensation of N-tosylimines with acyldiazomethanes. The diazo decomposition of these diazo carbonyl compounds under various catalytic conditions, including Rh(II) carboxylates, Cu(I) and Cu(II) complexes, PhCO2Ag/Et3N, TsOH, and SnCl2.2H(2)O, has been investigated. It was found that, in most cases, the diazo decomposition gave preferentially 1,2-aryl migration product, but 1,2-hydride migration predominated when PhCO2Ag/Et3N was the catalytic system. Hammett correlation has been applied in the analysis of the electronic effects of 1,2-aryl migration. The factors that govern the migratory preference and the mechanistic aspects of the reaction are discussed.