Reactivity and kinetic–mechanistic studies of regioselective reactions of rhodium porphyrins with unactivated olefins in water that form β-hydroxyalkyl complexes and conversion to ketones and epoxides†,10.1039/B912219B

热搜：

Lactoyl-CoA 全氟丁基戊烷白叶藤碱全氟己基辛烷新白叶藤碱壳寡糖特色专题-生物多肽

Reactivity and kinetic–mechanistic studies of regioselective reactions of rhodium porphyrins with unactivated olefins in water that form β-hydroxyalkyl complexes and conversion to ketones and epoxides†

Jiadi Zhang,Bradford B. Wayland,Lin Yun,Shan Li,Xuefeng Fu

Dalton Transactions Pub Date : 10/22/2009 00:00:00 , DOI:10.1039/B912219B

Abstract

This article reports on the selective oxidation of unactivated alkenes to ketones and epoxides through the intermediacy of β-hydroxyalkyl rhodium porphyrin complexes which are formed by reactions of terminal alkenes with tetra(p-sulfonatophenyl)porphyrin rhodium(III) complex. The β-hydroxyalkyl rhodium porphyrin complexes in water undergo β-C–H elimination to produce ketones in aqueous pH 9.0 solutions and O–H deprotonation in KOH/DMSO solutions resulting in the rapid and quantitative intramolecular nucleophilic displacement to form 1,2-epoxyalkanes.