ISOMERIZATION OF (PI-ALLYL)PALLADIUM COMPLEXES VIA NUCLEOPHILIC DISPLACEMENT BY PALLADIUM(0) - A COMMON MECHANISM IN PALLADIUM(0)-CATALYZED ALLYLIC SUBSTITUTION

被引：222

作者：

GRANBERG, KL ^{[1
]}

BACKVALL, JE ^{[1
]}

机构：

[1] UNIV UPPSALA,DEPT ORGAN CHEM,BOX 531,S-75121 UPPSALA,SWEDEN

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1992年 / 114卷 / 17期

关键词：

D O I：

10.1021/ja00043a034

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Treatment of (pi-allyl)palladium complexes such as 6 and 9 with Pd(PPh3)4 leads to rapid isomerization at -15-degrees-C in tetrahydrofuran and other solvents. At 0-degrees-C and in the presence of more than 2 equiv of triphenylphosphine per palladium, the phosphine attacks the pi-allyl group to give allylic phosphonium salts 7 with concomitant formation of a palladium(0)-phosphine complex, and isomerization of 6 is observed. Attack by PPh3 on 6 was shown to be stereospecific and to proceed with inversion. Studies of the Pd(0)-catalyzed substitution of 1c (X = OAc) with several different nucleophiles support the hypothesis that Pd(0) acts as a nucleophile on (pi-allyl)palladium complexes, in a reaction that leads to loss of stereospecificity in these systems.

引用

页码：6858 / 6863

页数：6

共 42 条

[1] ROLE AND EFFECTS OF HALIDE-IONS ON THE RATES AND MECHANISMS OF OXIDATIVE ADDITION OF IODOBENZENE TO LOW-LIGATED ZEROVALENT PALLADIUM COMPLEXES PD0(PPH3)2 [J].

AMATORE, C ;

AZZABI, M ;

JUTAND, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (22) :8375-8384

[2] MECHANISM OF OXIDATIVE ADDITION OF PALLADIUM(0) WITH AROMATIC IODIDES IN TOLUENE, MONITORED AT ULTRAMICROELECTRODES [J].

AMATORE, C ;

PFLUGER, F .

ORGANOMETALLICS, 1990, 9 (08) :2276-2282

[3]

BACKVALL JE, 1991, ISRAEL J CHEM, V31, P17

[4] PALLADIUM-CATALYZED CIS-ANNULATION AND TRANS-ANNULATION TO 1,3-CYCLOHEXADIENE AND 1,3-CYCLOHEPTADIENE [J].

BACKVALL, JE ;

VAGBERG, JO ;

GRANBERG, KL .

TETRAHEDRON LETTERS, 1989, 30 (05) :617-620

[5]

BACKVALL JE, 1984, J AM CHEM SOC, V106, P4369

[6]

BACKVALL JE, 1990, NEW J CHEM, V14, P447

[7]

BACKVALL JE, 1985, J AM CHEM SOC, V107, P6892

[8]

BACKVALL JE, 1985, J AM CHEM SOC, V107, P3676

[9]

BACKVALL JE, 1984, J ORG CHEM, V49, P4619

[10]

BACKVALL JE, 1983, ORGANOMETALLICS, V2, P1625

← 1 2 3 4 5 →