Ruthenium complexes bearing bulky pentasubstituted cyclopentadienyl ligands and evaluation of [Ru(η5-C5Me4R)(MeCN)3][PF6] precatalysts in nucleophilic allylic substitution reactions

被引：8

作者：

Zhang, Hui-Jun ^{[1
,2
]}

Demerseman, Bernard ^{[2
]}

Xi, Zhenfeng ^{[1
]}

Bruneau, Christian ^{[2
]}

机构：

[1] Peking Univ, Coll Chem, Minist Educ, Key Lab Bioorgan Chem & Mol Engn,BNLMS, Beijing 100871, Peoples R China

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

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2008年 / 20期

关键词：

allylation; cyclopentadienyl ligands; homogeneous catalysis; regioselectivity; ruthenium; metallocenes;

D O I：

10.1002/ejic.200800295

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

[Ru(eta(5)-C5Me4R)(MeCN)(3)][PF6] (R = CH(2)tBu, iPr, tBu, and CF3; 2-5) complexes were synthesized in two steps starting from the appropriate cyclopentadienes and RuCl3 center dot 3H(2)O. The fully substituted ruthenocenes [Ru(C5Me5)(C5Me4R*)], [Ru(C5Me5)(C(5)nPr(4)R*)] {R* = (lR,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl} and [Ru(C5Me5)(C(5)nPr(5))] were obtained by treating [Ru(C5Me5)Cl](4) with the corresponding cyclopentadienyllithiurn salts. Complexes 2-5 were evaluated as catalyst precursors for nucleophilic allylic substitution reactions, and the results were compared to those obtained with the [Ru(C5Me5)(MeCN)(3)][PF6] (1) precatalyst. The etherification of p-methoxyphenol with the typical aliphatic chlorohexene allylic substrate shows that the introduction of the bulky tert-butyl and trifluoromethyl groups into the tetramethylcyclopentadienyl ring results in a valuable enhancement in regioselectivity in favour of the branched allyl aryl ether. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

引用

页码：3212 / 3217

页数：6

共 45 条

[1] Octa- and nonamethylfluorene and an electron-rich permethylfluorenyl ruthenocene derivative [J].

Bazinet, Patrick ;

Tupper, Karl A. ;

Tilley, T. Don .

ORGANOMETALLICS, 2006, 25 (18) :4286-4291

[2] Pentamethylcyclopentadienyl-ruthenium catalysts for regio- and enantioselective allylation of nucleophiles [J].

Bruneau, Christian ;

Renaud, Jean-Luc ;

Demerseman, Bernard .

CHEMISTRY-A EUROPEAN JOURNAL, 2006, 12 (20) :5178-5187

[3] 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

[4] Synthesis of ruthenium complexes with planar-chiral cyclopentadienyl-pyridine or -phosphine bidentate ligands [J].

Dodo, N ;

Matsushima, Y ;

Uno, M ;

Onitsuka, K ;

Takahashi, S .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2000, (01) :35-41

[5] Synthesis, structure, and reactivity of the methoxy-bridged dimer [Cp∧Ru(μ-OMe)]2 (Cp∧ = η5-1-methoxy-2,4-di-tert-butyl-3-neopentylcyclopentadienyl) [J].

Dutta, Barnali ;

Scopelliti, Rosario ;

Severin, Kay .

ORGANOMETALLICS, 2008, 27 (03) :423-429

[6] Ruthenium half-sandwich complexes with sterically demanding cyclopentadienyl Ligands [J].

Dutta, Barnali ;

Solari, Euro ;

Gauthier, Sebastien ;

Scopelliti, Rosario ;

Severin, Kay .

ORGANOMETALLICS, 2007, 26 (19) :4791-4799

[7] A facile route to 1-trifluoromethyl-2,3,4,5-tetramethylcyclopentadienyl ruthenium half- and mixed-sandwich compounds [J].

Evju, JK ;

Mann, KR .

ORGANOMETALLICS, 2002, 21 (05) :993-996

[8] MOLECULAR ENGINEERING OF SOLID-STATE MATERIALS - ORGANOMETALLIC BUILDING-BLOCKS [J].

FAGAN, PJ ;

WARD, MD ;

CALABRESE, JC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (05) :1698-1719

[9] SYNTHESIS AND UNUSUAL PROPERTIES OF A HELICALLY TWISTED MULTIPLY METALATED RUBRENE DERIVATIVE [J].

FAGAN, PJ ;

WARD, MD ;

CASPAR, JV ;

CALABRESE, JC ;

KRUSIC, PJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (09) :2981-2983

[10] MANIPULATION OF ORGANOACTINIDE COORDINATIVE UNSATURATION - SYNTHESIS, STRUCTURES, AND REACTIVITY OF THORIUM HYDROCARBYLS AND HYDRIDES WITH CHELATING BIS(TETRAMETHYLCYCLOPENTADIENYL) ANCILLARY LIGANDS [J].

FENDRICK, CM ;

SCHERTZ, LD ;

DAY, VW ;

MARKS, TJ .

ORGANOMETALLICS, 1988, 7 (08) :1828-1838

← 1 2 3 4 5 →