Diastereoselectivity in enolate coordination in a new class of chiral ruthenium enolate complexes

被引：28

作者：

Rasley, BT ^{[1
]}

Rapta, M ^{[1
]}

Kulawiec, RJ ^{[1
]}

机构：

[1] GEORGETOWN UNIV,DEPT CHEM,WASHINGTON,DC 20057

来源：

ORGANOMETALLICS | 1996年 / 15卷 / 13期

关键词：

D O I：

10.1021/om960224j

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The new chiral carbon-bound enolate complexes Cp(CO)Ru(eta(2)(P,C)-Ph(2)PC(6)H(4)-o-C(O)CHR), where R = H (5a) or CH3 (5b), are formed via deprotonation. of the corresponding cationic Ketone complex precursors with LiN(Pr-i)(2). The latter species is formed diastereo-selectively, and the major diastereomer (S-Ru,R(C)/R(Ru),S-C) has been structurally characterized by X-ray crystallography. Deprotonation of the ethyl ketone complex with KO(t)Bu affords the O-bound analog (6), which converts to the C-bound form (5b) in the presence of LiOSO2CF3. Reaction of 5a with CH3OSO2CF3 forms the methyl enol ether complex by selective O-alkylation.

引用

收藏

页码：2852 / 2854

页数：3

相关论文

共 29 条

[1] RUTHENIUM AND OSMIUM COMPLEXES CONTAINING CYCLOPENTADIENYL AND RELATED PENTA-HAPTO DIENYL LIGANDS [J].

ALBERS, MO ;

ROBINSON, DJ ;

SINGLETON, E .

COORDINATION CHEMISTRY REVIEWS, 1987, 79 (1-2) :1-96

[2]

[Anonymous], ADV ORGANOMET CHEM

[3] TRANSITION-METAL ENOLATE CHEMISTRY - FORMATION OF A PALLADIUM ALKYL COMPLEX FROM A HIGHLY REACTIVE ENOLATOPALLADIUM COMPLEX [J].

BALEGROUNE, F ;

GRANDJEAN, D ;

LAKKIS, D ;

MATT, D .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1992, (15) :1084-1085

[4] CARBON CARBON BOND FORMING REACTIONS OF ORGANOTRANSITION METAL ENOLATE COMPLEXES [J].

BURKHARDT, ER ;

DONEY, JJ ;

SLOUGH, GA ;

STACK, JM ;

HEATHCOCK, CH ;

BERGMAN, RG .

PURE AND APPLIED CHEMISTRY, 1988, 60 (01) :1-6

[5] TUNGSTEN AND MOLYBDENUM 2-OXAALLYL (ETA-1-(C)-ENOLATE) COMPLEXES - FUNCTIONAL-GROUP TRANSFORMATIONS, PHOTOCHEMICAL ALDOL REACTIONS, AND ALKYNE/CO MIGRATORY INSERTION REACTIONS [J].

BURKHARDT, ER ;

DONEY, JJ ;

BERGMAN, RG ;

HEATHCOCK, CH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (07) :2022-2039

[6] HALF-SANDWICH CHIRAL RUTHENIUM COMPLEXES [J].

CONSIGLIO, G ;

MORANDINI, F .

CHEMICAL REVIEWS, 1987, 87 (04) :761-778

[7] PREPARATION AND PROPERTIES OF "DICARBONYL-H5-CYCLO-PENTADIENYLIRON VINYL-H-2 ETHER AND KETENE-H-2 ACETAL COMPLEXES [J].

CUTLER, A ;

RAGHU, S ;

ROSENBLU.M .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1974, 77 (03) :381-391

[8] SYNTHESIS AND REACTIVITY OF (ETA(6)-ARENE)(PHOSPHINO ENOLATO)RUTHENIUM(II) COMPLEXES, THEIR COUPLING REACTION WITH PHENYLACETYLENE, AND THERMAL REARRANGEMENT TO A PHOSPHAMETALLACYCLOPROPANE - X-RAY CRYSTAL-STRUCTURES OF (RU[ETA(3)-CH=C(PH)CH(PPH2)C(BUT)=O](P-CYMENE))(PF6), OF (RU[ETA(3)-CH=C(PH)C(ME)(PPH2)C(ET)=O](MESITYLENE))(BF4), AND OF (RU[ETA(3)-CH(PPH2)CPH=C(H)C(BUT)=O](MESITYLENE))(BF4) [J].

DEMERSEMAN, B ;

GUILBERT, B ;

RENOUARD, C ;

GONZALEZ, M ;

DIXNEUF, PH ;

MASI, D ;

MEALLI, C .

ORGANOMETALLICS, 1993, 12 (10) :3906-3917

[9] OXYGEN-BOUND AND CARBON-BOUND RUTHENIUM ENOLATES - MIGRATORY INSERTION, REDUCTIVE ELIMINATION, BETA-HYDROGEN ELIMINATION, AND CYCLOMETALLATION REACTIONS [J].

HARTWIG, JF ;

BERGMAN, RG ;

ANDERSEN, RA .

ORGANOMETALLICS, 1991, 10 (09) :3326-3344

[10] SYNTHESIS OF (PME3)4RU(ME)(OC(CH2)ME) AS AN EQUILIBRIUM MIXTURE OF OXYGEN-BOUND AND CARBON-BOUND TRANSITION-METAL ENOLATES - THERMAL ELIMINATION OF METHANE TO FORM AN ETA-4-OXATRIMETHYLENEMETHANE COMPLEX [J].

HARTWIG, JF ;

ANDERSEN, RA ;

BERGMAN, RG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (14) :5670-5671