Catalytic transformations of diazo compounds promoted by platinum(0) and dicationic platinum(II) complexes
作者:Roberta Bertani、Monica Biasiolo、Katia Darini、Rino A Michelin、Mirto Mozzon、Fabiano Visentin、Livio Zanotto
DOI:10.1016/s0022-328x(01)01082-8
日期:2002.1
9-Diazofluorene (DAF) is decomposed either stoichiometrically or catalytically in the presence of the platinum(0) complex [Pt(C2H4)(PPh3)2] to give difluoren-9-ylidene-hydrazine in high yield. Under analogous reaction conditions, diphenyldiazomethane gives mostly the azine, Ph2CNNCPh2, while ethyl diazoacetate (EDA) affords, in low yield, a mixture of diethyl fumarate and maleate in approximately
在铂(0)络合物[Pt(C 2 H 4)(PPh 3)2 ]存在下,化学计量或催化分解9-重氮芴(DAF),以高收率得到二芴9-亚甲基-肼。在类似的反应条件,二苯基重氮甲烷给出大多吖嗪中,Ph 2 CNNCPh 2,而重氮基乙酸乙酯(EDA),得到,在产量低,富马酸二乙酯和马来酸盐的在大约10:1混合物的摩尔比。苯乙烯与EDA的环丙烷化反应由一系列[PtL 2(NCCH 3)2 ] [Y] 2(L 2 = 2PPh3,Ph 2 PCH = CHPPh 2,Ph 2 PCH 2 CH 2 PPh 2;在60°C下于1,2-二氯乙烷中的Y = BF 4,CF 3 SO 3)保持24小时。DAF和EDA经历插入反应成醇ROH(R =甲基,乙基,的OH键吨-Bu,CH 2 CHCH 2中,Ph),在25℃在CH 2氯2 -ROH(DAF或EDA -ROH摩尔比1/20)在1%mol的几种