Electronic differentiations in palladium alkene complexes:: trans-phosphine preference of allylic leaving groups

被引：28

作者：

Goldfuss, B ^{[1
]}

Kazmaier, U ^{[1
]}

机构：

[1] Univ Heidelberg, Inst Organ Chem, D-69120 Heidelberg, Germany

来源：

TETRAHEDRON | 2000年 / 56卷 / 35期

关键词：

allylic substitutions; memory effects; Pd-complexes; computer-assisted methods;

D O I：

10.1016/S0040-4020(00)00613-X

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

B3LYP-computations of (Cl-)(PH3)Pd-alkene complexes reveal a distinct preference for arrangements with trans-phosphine situated allylic chlorine atoms (e.g. for E-2-chloropent-3-ene 1.6 kcal/mol in the gas phase and 1.5 kcal/mol in THF solution). Geometrical analyses show that Pd-alkene complexes with trans-phosphine positioned allylic chlorine atoms exhibit more strongly evolved allylic character than the analog cis-phosphine complexes. These differentiations, caused by the Pd-ligands (i.e. Cl-, PH3), represent electronic origins for memory effects in Pd-catalyzed allylic substitutions. (C) 2000 Elsevier Science Ltd. All rights reserved.

引用

页码：6493 / 6496

页数：4

共 38 条

[1] Anionic Pd(0) and Pd(II) intermediates in palladium-catalyzed Heck and cross-coupling reactions [J].

Amatore, C ;

Jutand, A .

ACCOUNTS OF CHEMICAL RESEARCH, 2000, 33 (05) :314-321

[2] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[3] First-principles investigation of enantioselective catalysis: Asymmetric allylic amination with Pd complexes bearing P,N-ligands [J].

Blochl, PE ;

Togni, A .

ORGANOMETALLICS, 1996, 15 (20) :4125-4132

[4] CONFORMATIONAL-ANALYSIS OF CHIRAL ALKENES AND OXONIUM IONS - ABINITIO MOLECULAR-ORBITAL CALCULATIONS AND AN IMPROVED MM2 FORCE-FIELD [J].

BROEKER, JL ;

HOFFMANN, RW ;

HOUK, KN .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (13) :5006-5017

[5] Robust and catalytically active mono- and bis-Pd-complexes of the 'Trost modular ligand' [J].

Butts, CP ;

Crosby, J ;

Lloyd-Jones, GC ;

Stephen, SC .

CHEMICAL COMMUNICATIONS, 1999, (17) :1707-1708

[6] Ab initio study of solvated molecules: A new implementation of the polarizable continuum model [J].

Cossi, M ;

Barone, V ;

Cammi, R ;

Tomasi, J .

CHEMICAL PHYSICS LETTERS, 1996, 255 (4-6) :327-335

[7]

COTTON FA, 1998, ADV INORG CHEM, P1299

[8] A SET OF F-POLARIZATION FUNCTIONS FOR PSEUDO-POTENTIAL BASIS-SETS OF THE TRANSITION-METALS SC-CU, Y-AG AND LA-AU [J].

EHLERS, AW ;

BOHME, M ;

DAPPRICH, S ;

GOBBI, A ;

HOLLWARTH, A ;

JONAS, V ;

KOHLER, KF ;

STEGMANN, R ;

VELDKAMP, A ;

FRENKING, G .

CHEMICAL PHYSICS LETTERS, 1993, 208 (1-2) :111-114

[9] TO WHAT EXTENT IS A PI-ALLYLIC INTERMEDIATE INVOLVED IN SOME PALLADIUM-CATALYZED ALKYLATIONS [J].

FIAUD, JC ;

MALLERON, JL .

TETRAHEDRON LETTERS, 1981, 22 (15) :1399-1402

[10]

Frisch M.J., 1998, GAUSSIAN 98

← 1 2 3 4 →