Chiral-at-metal complexes and their catalytic applications in organic synthesis

被引:251
作者
Bauer, Eike B. [1 ]
机构
[1] Univ Missouri, Dept Chem & Biochem, St Louis, MO 63121 USA
关键词
DIELS-ALDER REACTIONS; 1,3-DIPOLAR CYCLOADDITION; RUTHENIUM(II) COMPLEXES; RHODIUM; CONFIGURATION; COORDINATION; STABILITY; CENTERS; LIGANDS; STEREOCHEMISTRY;
D O I
10.1039/c2cs15234g
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
This tutorial review provides an introduction to the synthesis and characterization of chiral-at-metal complexes and their catalytic application in organic transformations. The synthetic access to these architectures either via chiral resolution or by employment of chiral ligands is described, characterization techniques for the complexes are referenced and the application of the R/S nomenclature is explained. Racemization and epimerization processes are often observed for the title compounds; the article gives mechanistic insights to these processes and describes how to recognize and document them. Finally, key catalytic applications in organic synthesis are presented and how the molecular architectures of the chiral-at-metal complexes lead to stereodifferentiation and, thus to enantiomeric excesses in the products.
引用
收藏
页码:3153 / 3167
页数:15
相关论文
共 60 条
[1]  
Aghossou F., 1992, INORG SYNTH, V29, P211
[2]   Ruthenium-catalyzed asymmetric electrophilic fluorination of 1,3-dicarbonyl compounds [J].
Althaus, Martin ;
Becker, Claus ;
Togni, Antonio ;
Mezzetti, Antonio .
ORGANOMETALLICS, 2007, 26 (24) :5902-5911
[3]   Differentiation of planar chiral enantiomers of [Cp*M(2-alkyl-Phenoxo)] [BF4] {M = Rh, Ir} by the trisphat anion [J].
Amouri, H ;
Thouvenot, R ;
Gruselle, M .
COMPTES RENDUS CHIMIE, 2002, 5 (04) :257-262
[4]   METALLACYCLES WITH STEREOGENIC METAL CENTERS - SYNTHESIS AND CHARACTERIZATION OF DIASTEREOMERIC CYCLORUTHENATED CHIRAL AMINES [J].
ATTAR, S ;
NELSON, JH ;
FISCHER, J ;
DECIAN, A ;
SUTTER, JP ;
PFEFFER, M .
ORGANOMETALLICS, 1995, 14 (10) :4559-4569
[6]   Introduction: Enantioselective catalysis [J].
Bolm, C ;
Gladysz, JA .
CHEMICAL REVIEWS, 2003, 103 (08) :2761-2762
[7]   Optically active transition metal compounds .112. Synthesis of chiral carbonylnitrosylcobalt complexes with bidentate PP*, PN* and NN* ligands [J].
Brunner, H ;
Faustmann, P ;
Dietl, A ;
Nuber, B .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1997, 542 (02) :255-263
[8]   Optically active transition metal complexes.: 126.: ortho-metalated chiral-at-metal half-sandwich (η6-arene)ruthenium complexes are configurationally more labile at the metal center than described:: Correction of published papers [J].
Brunner, H ;
Zwack, T .
ORGANOMETALLICS, 2000, 19 (13) :2423-2426
[9]   NITROSYL-METAL COMPLEXES .9. CATIONIC AND NEUTRAL DERIVATIVES OF C5H5 MN(CO)2NO(+) ION [J].
BRUNNER, H .
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 1969, 368 (3-4) :120-&
[10]   THERMAL AND ELECTROCATALYTIC EPIMERIZATION AT IRON AS THE CHIRAL CENTER [J].
BRUNNER, H ;
FISCH, K ;
JONES, PG ;
SALBECK, J .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1989, 28 (11) :1521-1523