Rhodium-catalysed isomerisation of allylic alcohols in water at ambient temperature
Rhodium-catalysed isomerisation of allylic alcohols in water at ambient temperature
复制标题
DOI：
10.1039/c004964f
复制
发表时间：
2010-01-01
期刊：
影响因子：
9.8
通讯作者：
Martin-Matute, Belen
中科院分区：
文献类型：
--
作者：
Ahlsten, Nanna;Lundberg, Helena;Martin-Matute, Belen
描述了一种将烯丙醇转化为羰基化合物的环境友好方法。使用 [Rh(COD(CH(3)CN)(2)]BF(4) (2) 与 1,3,5-triaza-7-phosphaadamantane (PTA, 1) 结合作为水中的催化体系，可以在环境温度下使各种仲烯丙醇发生非常快速的氧化还原异构化。此外，一些伯烯丙醇可以异构化为相应的醛。 该活性络合物在某些情况下可以以低至 0.5 mol% 的催化剂负载量使用，由市售试剂原位形成。基于氘标记研究，提出了涉及金属烯酮中间体的初步机制。
An environmentally benign method for the transformation of allylic alcohols into carbonyl compounds is described. Using [Rh(COD(CH(3)CN)(2)]BF(4) (2) in combination with 1,3,5-triaza-7-phosphaadamantane (PTA, 1) as the catalytic system in water results in a very fast redox isomerisation of a variety of secondary allylic alcohols at ambient temperature. Also, some primary allylic alcohols can be isomerised into the corresponding aldehydes. The active complex, which in some cases can be used in catalyst loadings as low as 0.5 mol%, is formed in situ from commercially available reagents. Based on deuterium labelling studies, a tentative mechanism involving metal-enone intermediates is presented.