Allenes as carbon nucleophiles in intramolecular attack on (π-1,3-diene)palladium complexes:: Evidence for trans carbopalladation of the 1,3-diene

被引：30

作者：

Dorange, I ^{[1
]}

Löfstedt, J ^{[1
]}

Närhi, K ^{[1
]}

Franzén, J ^{[1
]}

Bäckvall, JE ^{[1
]}

机构：

[1] Stockholm Univ, Arrhenius Lab, Dept Organ Chem, S-10691 Stockholm, Sweden

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2003年 / 9卷 / 14期

关键词：

C-C coupling; carbopalladation; palladium; reaction mechanisms;

D O I：

10.1002/chem.200305056

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Reaction of allene-substituted cyclohexa- and cyclohepta-1,3-dienes with [PdCl2(PhCN)(2)] gave eta(3)-( 1,2,3)-cyclohexenyl- and eta(3)-(1,2,3)-cycloheptenylpalladium complexes. respectively. in which C-C bond formation between the allene and the 1.3-diene has occurred. Analysis of the (pi-allyl)palladium complexes by NMR spectroscopy. using reporter ligands, shows that the C-C bond formation has occurred by a trans carbopalladation involving nucleophilic attack by the middle carbon atom of the allene on a (pi-diene)palladium(n) complex. The stereochemistry of the (pi-allyl)palladium complexes was confirmed by benzoquinone-induced stereoselective transformations to allylic acetates.

引用

页码：3445 / 3449

页数：5

共 34 条

[1] 2D NOESY OF PALLADIUM PI-ALLYL COMPLEXES - REPORTER LIGANDS, COMPLEX DYNAMICS, AND THE X-RAY STRUCTURE OF [PD(ETA-3-C4H7)(BPY)](CF3SO3) (BPY = BIPYRIDINE) [J].

ALBINATI, A ;

KUNZ, RW ;

AMMANN, CJ ;

PREGOSIN, PS .

ORGANOMETALLICS, 1991, 10 (06) :1800-1806

[2] 2-DIMENSIONAL H-1 NOESY OF PD(II) PI-ALLYL COMPLEXES - THE CONCEPT OF REPORTER LIGANDS AND THE MOLECULAR-STRUCTURE OF [PD(ETA-3-CH2CCHCH2CH2CH2)(BIQUINOLINE)]CF3SO3 [J].

ALBINATI, A ;

AMMANN, C ;

PREGOSIN, PS ;

RUEGGER, H .

ORGANOMETALLICS, 1990, 9 (06) :1826-1833

[3] PALLADIUM-CATALYZED OXASPIROCYCLIZATIONS [J].

ANDERSSON, PG ;

NILSSON, YIM ;

BACKVALL, JE .

TETRAHEDRON, 1994, 50 (02) :559-572

[4] A new asymmetric Wacker-type cyclization and tandem cyclization promoted by Pd(II)-spiro bis(isoxazoline) catalyst [J].

Arai, MA ;

Kuraishi, M ;

Arai, T ;

Sasai, H .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (12) :2907-2908

[5]

BACKVALL JE, 1981, J AM CHEM SOC, V103, P4959

[6]

BACKVALL JE, 1993, J ORG CHEM, V58, P5445

[7]

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

[8]

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

[9]

Backvall JE, 1998, METAL-CATALYZED CROSS-COUPLING REACTIONS, P339

[10] PALLADIUM IN SOME SELECTIVE OXIDATION REACTIONS [J].

BACKVALL, JE .

ACCOUNTS OF CHEMICAL RESEARCH, 1983, 16 (09) :335-342

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