Stereospecific Diphosphination of Activated Acetylenes: A General Route to Backbone-Functionalized, Chelating 1,2-Diphosphinoethenes
作者:Deborah L. Dodds、Mairi F. Haddow、A. Guy Orpen、Paul G. Pringle、Gary Woodward
DOI:10.1021/om060716o
日期:2006.12.1
The reaction of 2a,b with HC⋮CZ give the corresponding R2PCHCZPR2 (5a,b). A mechanism is proposed that accounts for the cis stereospecificity and the regioselectivity of these diphosphinations. Treatment of [PtCl2(1,5-cod)] or [PdCl2(NCPh)2] with a selection of the diphosphines (3−5) gave the expected chelate complexes, four of which, [PtCl2(3b)], [PtCl2(4a)], [PtCl2(4c)], and [PdCl2(4a)], have had
对称diphosphanes - [R 2 P-PR 2 其中R =苯基(1A)中,Cy(1B),或卜吨(1C)}是由R的反应制得的2 PLI,其中R 2的PCl。不对称diphosphanes - [R 2 P-PR ' 2 其中R =卜吨和R'= Ph(上图2a); R = Bu t和R'= o- Tol(2b); R = Cy和R'= Ph(2c); R = Cy和R'= o- Tol(2d); R = Cy和R'= Bu t(2e)}是由R的反应制得的2 P(BH 3)与李R” 2,接着用Et脱保护的PCl 2 NH。Diphosphanes 1A,b和图2a - d与ZC⋮CZ(Z = CO反应2 Me)的,得到相应的R 2 PCZ CZPR 2(图3a,b)或R 2 PCZ CZPR” 2(图4a - d)。2a,b与HC⋮CZ的反应得到相应的R 2 PCH CZPR2(5