Polyfunctional phosphine ligands. Preparation of 4′-formyl-2-diphenylphosphinoacetophenone and its coordination properties
作者:Daravong Soulivong、Raymond Ziessel、Dominique Matt
DOI:10.1016/0022-328x(94)84067-9
日期:1994.7
[4′-CH(OC2H5)2}C6H4]CH(OH) CH3 (2). This is oxidized with MnO2 to yield the key ketone [4′-CH(OC2H5)2}C6H4]C(O)CH3 (3). Metallation of 3 with LiN[(CH3)3Si]2 and subsequent reaction with Ph2PCl affords the phosphine [4′-CH(OC2H5) 2}C6H4]C(O)CH2PPh2 (4) which after deprotection of the aldehyde function yields 5. Condensation of 5 with the p-substituted anilines H2NA-i and H2NA*-12 gives quantitatively the corresponding
三功能配体[4'-(CHO)C 6 H 4 ] C(O)CH 2 PPh 2(5)从对苯二甲醛单-(二乙基乙缩醛)(1)开始分四步制备(总收率50%):1与CH 3 MgBr的反应生成[4'-CH(OC 2 H 5)2 } C 6 H 4 ] CH(OH)CH 3(2)。将其用MnO 2氧化,得到键酮[4'-CH(OC 2 H 5)2 } C 6 H 4] C(O)CH 3(3)。3用LiN [(CH 3)3 Si] 2金属化,然后与Ph 2 PCl反应,得到膦[4'-CH(OC 2 H 5)2 } C 6 H 4 ] C(O)CH 2 PPh 2(4),其在醛官能团脱保护后产生5。5与对位取代苯胺H 2 NA-i和H 2的缩合NA * -12定量给出相应的膦亚胺6-9。化合物4与[Pd(acac)2 ]立即反应,定量生成双-(烯醇式)复合物顺式-[Pd 4'-[CH(OC 2