Selective hydroaminomethylation of olefins using simple and efficient Rh-phosphinite complex catalyst
作者:Shoeb R. Khan、Bhalchandra M. Bhanage
DOI:10.1002/aoc.3046
日期:2013.12
Hydroaminomethylation of various olefins with primary and secondary amines was carried out using a simple and efficient rhodium–phosphinite complexcatalyst. The influence of various reaction parameters including the effects of temperature, pressure, catalyst loading, time and solvents has been investigated. The present protocol is general with wider substrate applicability for the synthesis of an
Synthesis and transition metal chemistry of a bridging diphosphinite, 1,4 bis(diphenylphosphinoxy)benzene
作者:Maravanji S. Balakrishna、D. Suresh、Pawan Kumar、Joel T. Mague
DOI:10.1016/j.jorganchem.2011.08.008
日期:2011.11
Diphosphinite ligand, [Ph2POC6H4OPPh2] (1), is obtained by reacting chloro diphenylphosphine, with 1,4-dihydroxy benzene in presence of triethylamine. Treatment of 1 with elemental sulfur or selenium resulted in the formation of bis(chalcogenide) derivatives, [Ph-2(E)POC6H4OP(E)Ph-2] (2, E = S; 3, E = Se) in almost quantitative yield. The binuclear complex [(eta(6)-p-cymene)RuCl2}(2)(Ph2POC6H4OPPh2)] (4) is produced in the reaction between [Ru(eta(6)-p-cymene)Cl-2](2) and diphosphinite 1. Similarly the reaction of 1 with [Rh(COD)Cl](2) afforded a binuclear complex [(COD)RhCl}(2)(Ph2POC6H4OPPh2)] (5), whereas the macrocyclic complex [(CO)RhCl}(Ph2POC6H4OPPh2)](2) (6) is isolated in the reaction of 1 with 0.5 equiv of [RhCl(CO)(2)](2). Compound 1 on treatment with [Pd(COD)Cl-2] or [PdCl2(SMe2)(2)] in 1:1 molar ratio produced the chloro-bridged binuclear complex [(PPh2O)Pd(mu-Cl)(PPh2OH)}(2)] (7) through P-O bond cleavage. Treatment of 1 with two equivalents of CuI in dichlormethane/acetonitrile (1:1) afforded a coordination polymer, [Cu-2(mu-I)(2)(Ph2POC6H4OPPh2)}(infinity)] (8) in moderate yield. The binuclear complex, [AuCl}(2)(mu-Ph2POC6H4OPPh2)] (9) is obtained in the reaction of compound 1 with two equiv of AuCl(SMe2), where the ligand exhibits bridged bidentate mode of coordination. The molecular structures of 1-4, and 6 are determined by X-ray diffraction studies. (C) 2011 Elsevier B.V. All rights reserved.