2-Thioanisyldichlorophosphine, new starting material for the preparation of multidentate phosphine ligands: syntheses and characterization of derivatives of 2-anisyl- and 2-thioanisyldichlorophosphines
作者:Riitta H. Laitinen、Ville Heikkinen、Matti Haukka、Ari M.P. Koskinen、Jouni Pursiainen
DOI:10.1016/s0022-328x(99)00711-1
日期:2000.4
A new aryldichlorophosphine, 2-thioanisyldichlorophosphine, and its anisyl analogue, 2-anisyldichlorophosphine, were prepared by using an organozinc halide reagent of 2-thioanisole or 2-anisole with ethereal solution of PCl3 in refluxing conditions. From these aryldichlorophosphines, eight new multidentate phosphine ligands containing 2-thioanisyl, 4-thioanisyl, 2-anisyl, 1-naphthyl and 9-anthracenyl groups were synthesized and characterized. Characterization was based mainly on NMR spectroscopy and X-ray crystallography. The crystal structures of six ligands are reported. The electronic effects on basicity of ligands are discussed. (C) 2000 Elsevier Science S.A. All rights reserved.
The present invention concerns a process for preparing substituted arylhalophosphines and derivatives thereof. According to the invention a substituted haloaryl is lithiated to form a substituted lithiumaryl which is subjected to metal exchange to provide a metal exchanged organometal compound. After reaction with a halophosphine compound a substituted aryl halophosphine is obtained. The present invention also provides a novel process for hydroformylation of olefinic compounds. The hydroformylation is carried out in the presence of a catalyst system based on a rhodium precursor and heterodonor ligands of the formula (I): YX1X2X3, wherein Y is phosphorus or arsenic and X1, X2 and X3 are each independently selected from aromatic groups comprising substituted phenyl and pyridyl groups, the substituents being hydrocarbyl groups attached to the aromatic ring at ortho-position via a heteroatom. With the various ligands of the present invention, i/n-ratios in range of 5 to 30 are obtainable. In the case of hydroformylation of methyl methacrylate, the selectivity of the methyl α-formylisobutyrate is 80 - 90 % and the amount of byproducts, such as methyl isobutyrate, is small.
Synthesis and applications to asymmetric catalysis of a series of mono- and bis(diazaphospholidine) ligands
作者:Donald Smyth、Heather Tye、Colin Eldred、Nathaniel W. Alcock、Martin Wills
DOI:10.1039/b106399p
日期:2001.11.1
The synthesis of a series of closely related mono- and bis(diazaphospholidine) ligands has been achieved using the condensation of a diamine with a bis(dimethylamino)arylphosphine. The resulting ligands have given excellent results in palladium-catalysed allylic substitution reactions to form C–C bonds (up to 89% ee) and C–N bonds (up to 78% ee).