Pentamethylcyclopentadienyl-ruthenium catalysts for regio- and enantioselective allylation of nucleophiles

被引：118

作者：

Bruneau, Christian ^{[1
]}

Renaud, Jean-Luc ^{[1
]}

Demerseman, Bernard ^{[1
]}

机构：

[1] Univ Rennes 1, UMR 6226, CNRS, F-35042 Rennes, France

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2006年 / 12卷 / 20期

关键词：

allylation; enantioselectivity; nucleophilic substitution; regioselectivity; ruthenium;

D O I：

10.1002/chem.200600173

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Ruthenium(II) complexes containing the pentamethylcyclopentadienyl ligand efficiently perform the activation of allylic carbonates and halides to generate cationic and dicationic ruthenium(IV) complexes. This activation has been transferred as a key step to the catalytic allylation of nucleophiles. The structural and electronic properties of the allylic moieties lead to the regioselective formation of chiral products resulting from nucleophilic addition to their most substituted terminus. The catalytic activity of various Ru(Cp*) precatalysts in several allylic substitutions by C and 0 nucleophiles will be presented. The enantioselective version that has been demonstrated by using optically pure bisoxazoline ligands will also be discussed.

引用

页码：5178 / 5187

页数：10

共 71 条

[1]

[Anonymous], ANGEW CHEM

[2]

[Anonymous], RUTHENIUM ORGANIC SY

[3]

[Anonymous], PADDADIUM REAGENTS C

[4] Molybdenum-catalyzed asymmetric allylic alkylations [J].

Belda, O ;

Moberg, C .

ACCOUNTS OF CHEMICAL RESEARCH, 2004, 37 (03) :159-167

[5]

BRUNEAU C, 2006, IN PRESS TOP ORGANOM

[6] Ruthenium-catalyzed stereospecific decarboxylative allylation of non-stabilized ketone enolates [J].

Burger, EC ;

Tunge, JA .

CHEMICAL COMMUNICATIONS, 2005, (22) :2835-2837

[7] Ruthenium-catalyzed decarboxylative allylation of nonstabilized ketone enolates [J].

Burger, EC ;

Tunge, JA .

ORGANIC LETTERS, 2004, 6 (15) :2603-2605

[8] Synthesis and reactivity of [Ru(Cp*)(L)(MeCN)2][PF6] (L = Ph2POMe or Ph2P-o-tolyl) and {Ru(Cp*)[Ph2PCH2C(tBu)=O](MeCN)}[PF6] complexes, their involvement as catalyst precursors for regioselective allylic substitution reactions and related [Ru(Cp*)Cl(Ph2POMe)(RCHCHCH2)][PF6] η3-allyl ruthenium(IV) intermediates [J].

Demerseman, B ;

Renaud, JL ;

Toupet, L ;

Hubert, C ;

Bruneau, C .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2006, (07) :1371-1380

[9]

Dömling A, 2000, ANGEW CHEM INT EDIT, V39, P3168, DOI 10.1002/1521-3773(20000915)39:18<3168::AID-ANIE3168>3.0.CO

[10]

2-U

← 1 2 3 4 5 6 7 8 →