Synthesis of New Mixed Phosphine∼Iminophosphorane Bidentate Ligands and Their Coordination to Group 10 Metal Centers
作者:Leïla Boubekeur、Louis Ricard、Nicolas Mézailles、Pascal Le Floch
DOI:10.1021/om0490684
日期:2005.3.1
Ph, nBu, α(+)-Me-benzyl). These salts were then deprotonated quantitatively to yield the desired new phosphine−iminophosphorane ligands 4a−e (P∼PNR). This simple strategy allows for a wide variation of the R substituent at the nitrogen donor group (R = alkyl, aryl, benzyl). In particular, the optically pure ligand 4e (R = α(+)-Me-benzyl) was obtained in one pot from commercially available α(+)-Me-benzylamine
对称双齿二膦的选择性monobromation(DPPM =双- diphenylphosphinomethane),得到高反应性的中间产物,2(P~PBr + ·溴- ),则报告。捕获的两个方法分别设计以产生混合的膦-氨基鏻盐3(P~PNHR + ·溴- )。第一种方法依赖于反应2与2当量的伯胺,得到图3a - Ç(P~PNHR + ·溴-,R = P-ME-BN,对-的MeO-BN,PH)。第二种方法利用1当量的伯胺和DABCO作为捕集剂,得到3a - e(P〜PNHR+ ·溴-,R = P-ME-BN,对-的MeO-BN,PH,Ñ卜,α(+) -我-苄基)。然后将这些盐定量去质子化,得到所需的新膦-亚氨基正膦配体4a - e(P〜PNR)。这种简单的策略允许在氮供体基团(R =烷基,芳基,苄基)上的R取代基有很大的变化。特别地,在一锅中从市售的α(+)-Me-苄基胺获得光学纯的配体4e(R