Transposition of allylic alcohols into carbonyl compounds mediated by transition metal complexes.
Transposition of allylic alcohols into carbonyl compounds mediated by transition metal complexes.
复制标题
DOI：
10.1021/cr0103165
复制
发表时间：
2003
期刊：
影响因子：
62.1
通讯作者：
R. Uma;C. Crévisy;R. Grée
中科院分区：
文献类型：
--
作者：
R. Uma;C. Crévisy;R. Grée
烯丙醇转化为饱和羰基化合物是一个有用的合成过程，通常需要两步连续氧化和还原反应。一锅催化转化（方案1），相当于一个内部氧化还原过程，是一个概念上有吸引力的策略。除了在过程中保持总原子经济性外，4还可以避免使用昂贵和/或有毒的试剂，特别是在氧化反应中。在这方面，已经开发了许多方法，利用过渡金属配合物迁移双键的能力。在烯丙醇的情况下，这种迁移将导致形成烯醇（或烯醇酯）中间体，通过互变异构可以产生饱和羰基化合物。5
The conversion of allylic alcohols to saturated carbonyl compounds is a useful synthetic process and would conventionally require a two-step sequential oxidation and reduction reactions. A one-pot catalytic transformation (Scheme 1), equivalent to an internal redox process, is a conceptually attractive strategy. 1-3 Apart from maintaining total atom economy in the process, 4 it could also avoid the use of costly and/or toxic reagents, especially in the oxidation reactions. In this regard, a number of methods have been developed harnessing the ability of transition metal complexes to migrate double bonds. Such a migration in the case of an allylic alcohol would result in the formation of an enol (or enolate) intermediate which on tautomerization can afford the saturated carbonyl compound. 5