Ruthenium-catalyzed allylic alkylation reactions:: Carbonate-based catalysts and intermediates

被引：69

作者：

Hermatschweiler, R ^{[1
]}

Fernández, I

Breher, F

Pregosin, PS

Veiros, LF

Calhorda, MJ

机构：

[1] ETH Honggerberg, Inorgan Chem Lab, CH-8093 Zurich, Switzerland

[2] Inst Super Tecn, Ctr Quim Estrutural, P-1049001 Lisbon, Portugal

[3] Univ Lisbon, Fac Ciencias, Dept Quim & Bioquim, P-1749016 Lisbon, Portugal

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2005年 / 44卷 / 28期

关键词：

allylic alkylation; carbonate complex; density functional calculations; ruthenium; structure elucidation;

D O I：

10.1002/anie.200500967

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

(Chemical Equation Presented) Branching out: A previously unrecognized ruthenium carbonate intermediate is formed during the reaction of an allylic tert-butoxycarbonate with the ruthenium complex [Ru(Cp*) (CH 3CN)3]PF6 (1; see scheme). The isolatable carbonate-allyl complex functions very effectively as an allylic alkylation catalyst. These results provide new insights into the mechanism of this ruthenium-catalyzed reaction. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：4397 / 4400

页数：4

共 22 条

[1]

[Anonymous], ANGEW CHEM

[2]

[Anonymous], ANGEW CHEM

[3] Conservation of absolute configuration in the acyclic rhodium-catalyzed allylic alkylation reaction:: Evidence for an enyl (σ+π) organorhodium intermediate [J].

Evans, PA ;

Nelson, JD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (22) :5581-5582

[4] Regioselective rhodium-catalyzed allylic alkylation with a modified Wilkinson's catalyst [J].

Evans, PA ;

Nelson, JD .

TETRAHEDRON LETTERS, 1998, 39 (13) :1725-1728

[5] X-ray, 13C NMR, and DFT studies on a ruthenium(IV) allyl complex.: Explanation for the observed control of regioselectivity in allylic alkylation chemistry [J].

Hermatschweiler, R ;

Fernández, I ;

Pregosin, PS ;

Watson, EJ ;

Albinati, A ;

Rizzato, S ;

Veiros, LF ;

Calhorda, MJ .

ORGANOMETALLICS, 2005, 24 (08) :1809-1812

[6] The first organoruthenium(IV) complexes containing nitrogen donor ligands by oxidative addition of allylic substrates to coordinatively unsaturated Ru(II) complexes [J].

Kondo, H ;

Yamaguchi, Y ;

Nagashima, H .

CHEMICAL COMMUNICATIONS, 2000, (12) :1075-1076

[7] NUCLEOPHILIC AND ELECTROPHILIC ALLYLATION REACTIONS - SYNTHESIS, STRUCTURE, AND AMBIPHILIC REACTIVITY OF (ETA(3)-ALLYL)RUTHENIUM(II) COMPLEXES [J].

KONDO, T ;

ONO, H ;

SATAKE, N ;

MITSUDO, T ;

WATANABE, Y .

ORGANOMETALLICS, 1995, 14 (04) :1945-1953

[8] Diastereoselective oxidative addition of allyl chloride to planar-chiral cyclopentadienyl-ruthenium complexes [J].

Matsushima, Y ;

Onitsuka, K ;

Takahashi, S .

ORGANOMETALLICS, 2004, 23 (16) :3763-3765

[9]

Mbaye M. D., 2003, ANGEW CHEM, V115, P5220

[10] [Cp*(η2-bipy)(MeCN)RuII][PF6] catalysts for regioselective allylic substitution and characterization of dicationic [Cp*(η2-bipy)(η3-allyl)RuIV][PF6]2 intermediates [J].

Mbaye, MD ;

Demerseman, B ;

Renaud, JL ;

Toupet, L ;

Bruneau, C .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (41) :5066-5068

← 1 2 3 →