BpCu-catalyzed cyclopropanation of olefins: A simple system that operates under homogeneous and heterogeneous conditions (Bp=dihydridobis(pyrazolyl)borate)

被引：65

作者：

Diaz-Requejo, MM ^{[1
]}

Nicasio, MC ^{[1
]}

Perez, PJ ^{[1
]}

机构：

[1] Univ Huelva, Dept Quim & Ciencia Mat, E-21819 Huelva, Spain

来源：

ORGANOMETALLICS | 1998年 / 17卷 / 14期

关键词：

D O I：

10.1021/om980061u

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The complexes BpCu (1), BpCuL (L = bipy, 2; L = Ph2PCH2CH2PPh2, 3; L = PCy3, 4) and BpCuL(2) (L = py, 5; L = PPh3, 6) catalyze the cyclopropanation of olefins in moderate to high yields in the homogeneous phase. These compounds can also be used under heterogeneous conditions, when supported on silica gel. Complex 1 converts an equimolar mixture of an olefin (styrene, cis-cyclooctene,1-hexene) and ethyl diazoacetate in the corresponding cyclopropanes in high yield with no excess of olefin employed. For the heterogeneous system, the catalysts can be recovered and reused several times (6-12 cycles) up to ca. 1000 turnovers. The data available suggest the existence of a common active species: the 14-electron BpCu fragment 1. These data consist of competition experiments with para-substituted styrenes as well as kinetic studies carried out in the presence and in the absence of the alkene.

引用

页码：3051 / 3057

页数：7

共 27 条

[1] SYNTHESIS AND CHARACTERIZATION OF NEW CHIRAL RH(I) COMPLEXES WITH N,N'-LIGANDS AND N,P-LIGANDS - A STUDY OF ANCHORING ON THE MODIFIED ZEOLITES AND CATALYTIC PROPERTIES OF HETEROGENIZED COMPLEXES [J].

CARMONA, A ;

CORMA, A ;

IGLESIAS, M ;

SANJOSE, A ;

SANCHEZ, F .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1995, 492 (01) :11-21

[2] Asymmetric cyclopropanations by rhodium(II) N-(arylsulfonyl)prolinate catalyzed decomposition of vinyldiazomethanes in the presence of alkenes. Practical enantioselective synthesis of the four stereoisomers of 2-phenylcyclopropan-1-amino acid [J].

Davies, HML ;

Bruzinski, PR ;

Lake, DH ;

Kong, N ;

Fall, MJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (29) :6897-6907

[3] Substituent effects on the reaction rates of copper-catalyzed cyclopropanation and aziridination of para-substituted styrenes [J].

Díaz-Requejo, MM ;

Perez, PJ ;

Brookhart, M ;

Templeton, JL .

ORGANOMETALLICS, 1997, 16 (20) :4399-4402

[4]

Doyle M. P., 1995, COMPREHENSIVE ORGANO, V12, P387

[5]

Doyle MP, 1997, CHEM COMMUN, P983

[6] Formation of macrocyclic lactones by enantioselective intramolecular cyclopropanation of diazoacetates catalyzed by chiral Cu-I and Rh-II compounds [J].

Doyle, MP ;

Peterson, CS ;

Parker, DL .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1996, 35 (12) :1334-1336

[7] BIS(OXAZOLINES) AS CHIRAL LIGANDS IN METAL-CATALYZED ASYMMETRIC REACTIONS - CATALYTIC, ASYMMETRIC CYCLOPROPANATION OF OLEFINS [J].

EVANS, DA ;

WOERPEL, KA ;

HINMAN, MM ;

FAUL, MM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (02) :726-728

[8] Cyclopropanation reactions catalysed by copper(II)-exchanged clays and zeolites. Influence of the catalyst on the selectivity [J].

Fraile, JM ;

Garcia, JI ;

Mayoral, JA .

CHEMICAL COMMUNICATIONS, 1996, (11) :1319-1320

[9] SEMICORRIN METAL-COMPLEXES AS ENANTIOSELECTIVE CATALYSTS .2. ENANTIOSELECTIVE CYCLOPROPANE FORMATION FROM OLEFINS WITH DIAZO-COMPOUNDS CATALYZED BY CHIRAL (SEMICORRINATO)COPPER COMPLEXES [J].

FRITSCHI, H ;

LEUTENEGGER, U ;

PFALTZ, A .

HELVETICA CHIMICA ACTA, 1988, 71 (06) :1553-1565

[10] Cyclopropanation of alkenes with ethyl diazoacetate catalysed by ruthenium porphyrin complexes [J].

Galardon, E ;

LeMaux, P ;

Simonneaux, G .

CHEMICAL COMMUNICATIONS, 1997, (10) :927-928

← 1 2 3 →