title: Methyltrioxorhenium-catalyzed highly selective dihydroxylation of 1,2-allenylic diphenyl phosphine oxides.
abstract: For the first time, methyltrioxorhenium (MTO) has been applied as a catalyst for the dihydroxylation of allenes in the presence of hydrogen peroxide as the oxidant. The regioselectivities turn out to be well controlled, affording β-carbonyl-γ-hydroxyl diphenyl phosphine oxides as the only product. The axial chirality of optically active allenes can also be nicely transferred to the chirality center of the products. Based on chirality transfer experiments and ESI-MS studies of (18)O-labeled products, a possible mechanism, proceeding via regioselective epoxidation of the electron-rich carbon-carbon double bond, a subsequent intermolecular nucleophilic attack of a water molecule on the in situ formed epoxide via neighboring group participation (NGP), followed by a rearrangement has been proposed as the major reaction pathway.
authors: School of Chemistry and Material Science, Liaoning Shihua University, Dandong Road 1, Fushun 113001, P. R. China. mingdong.zhou@lnpu.edu.cn.
authors: Junli
authors: J
authors: Hou
authors: Yang
authors: Y
authors: Chen
authors: Dongmei
authors: D
authors: Ma
authors: Burghard
authors: B
authors: Cordes
authors: Jingyun
authors: J
authors: Wang
authors: Xin
authors: X
authors: Wang
authors: Fritz E
authors: FE
authors: Kühn
authors: Hao
authors: H
authors: Guo
authors: Mingdong
authors: M
authors: Zhou