An unexpectedly stable chiral hydrido-solvent complex of Ru-II: A mechanistic link in the enantioselective hydrogenation of pyrones

被引：23

作者：

Currao, A ^{[1
]}

Feiken, N ^{[1
]}

Macchioni, A ^{[1
]}

Nesper, R ^{[1
]}

Pregosin, PS ^{[1
]}

Trabesinger, G ^{[1
]}

机构：

[1] ETH ZENTRUM,INORGAN CHEM LAB,CH-8092 ZURICH,SWITZERLAND

来源：

HELVETICA CHIMICA ACTA | 1996年 / 79卷 / 06期

关键词：

D O I：

10.1002/hlca.19960790608

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The ligand (6,6'-dimethoxybiphenyl-2,2'-diyl)bis[3,5-di(tert-butyl)phenylphosphine] (1) forms an unexpectedly stable hydrido-bis-solvento complex of composition [RuH(isopropanol)(2)(I)]BF4, (2) under the conditions used in the enantioselective hydrogenation of pyrones. The structure of 2, determined by X-ray diffraction, represents the first well-characterized chiral five-coordinate bis-phosphine ruthenium-hydride complex stable as a solvento complex, and provides a structural link in the enantioselective pyrone hydrogenation cycle catalyzed by [Ru(OAc)(2)(1)]. Using the arene complex [RuH(p-cymene)(1)]BF4 (3), the chiral pocket of coordinated 1 is shown to be relatively rigid, via NMR spectroscopy. This is reflected in restricted rotation about one of the four P-[3,5-di(tert-butyl)phenyl] P-C-ipso bonds at room temperature.

引用

页码：1587 / 1591

页数：5

共 24 条

[1] KINETICS AND MECHANISM OF CATALYSIS OF THE ASYMMETRIC HYDROGENATION OF ALPHA-BETA-UNSATURATED CARBOXYLIC-ACIDS BY BIS(CARBOXYLATO)(2,2'-BIS(DIPHENYLPHOSPHINO)-1,1'-BINAPHTHYL)-RUTHENIUM(II), [RUII(BINAP)(O2CR)2] [J].

ASHBY, MT ;

HALPERN, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (02) :589-594

[2] CRYSTAL AND MOLECULAR-STRUCTURE OF AN ASYMMETRIC HYDROGENATION CATALYST SUBSTRATE ADDUCT, DELTA-BIS(TIGLATO)((R)-2,2'-BIS(DIPHENYLPHOSPHINO)-1,1'-BINAPHTHYL)-RUTHENIUM(II), [RUII(BINAP)(O2CCME=CHME)2] [J].

ASHBY, MT ;

KHAN, MA ;

HALPERN, J .

ORGANOMETALLICS, 1991, 10 (06) :2011-2015

[3] 1,3-DIPHENYLALLYL COMPLEXES OF PALLADIUM(II) - NMR, X-RAY, AND CATALYTIC STUDIES [J].

BARBARO, P ;

PREGOSIN, PS ;

SALZMANN, R ;

ALBINATI, A ;

KUNZ, RW .

ORGANOMETALLICS, 1995, 14 (11) :5160-5170

[4] Chiral P,S-ligands based on beta-d-thioglucose tetraacetate. Palladium(II) complexes and allylic alkylation [J].

Barbaro, P ;

Currao, A ;

Herrmann, J ;

Nesper, R ;

Pregosin, PS ;

Salzmann, R .

ORGANOMETALLICS, 1996, 15 (07) :1879-1888

[5]

CASHMAN RSM, 1992, INORG CHEM, V31, P5509

[6]

GENET JP, 1995, ACROS ORGANICS ACTA, V1, P4

[7] PALLADIUM PI-ALLYL CHEMISTRY OF NEW P,S BIDENTATE LIGANDS - SELECTIVE BUT VARIABLE DYNAMICS IN THE ISOMERIZATION OF THE ETA(3)-C3H5 AND ETA(3)-PHCHCHCHPH PI-ALLYL LIGANDS [J].

HERRMANN, J ;

PREGOSIN, PS ;

SALZMANN, R ;

ALBINATI, A .

ORGANOMETALLICS, 1995, 14 (07) :3311-3318

[8] QUANTITATIVE EXPRESSION OF DYNAMIC KINETIC RESOLUTION OF CHIRALLY LABILE ENANTIOMERS - STEREOSELECTIVE HYDROGENATION OF 2-SUBSTITUTED 3-OXO CARBOXYLIC ESTERS CATALYZED BY BINAP-RUTHENIUM(II) COMPLEXES [J].

KITAMURA, M ;

TOKUNAGA, M ;

NOYORI, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (01) :144-152

[9]

KITAMURA M, 1989, MODERN SYNTHETIC MET, V5, P116

[10] SYNTHESIS AND CHARACTERIZATION OF MONONUCLEAR AND TRINUCLEAR RUTHENIUM COMPLEXES OF 2,2'-BIS(DIPHENYLPHOSPHINO)-1,1'-BINAPHTHYL AND THEIR CATALYTIC ACTIVITY [J].

MASHIMA, K ;

HINO, T ;

TAKAYA, H .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1992, (13) :2099-2107

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