Highly cis-Selective Rh(I)-Catalyzed Cyclopropanation Reactions

被引：37

作者：

Rosenberg, Marianne Lenes ^{[2
]}

Vlasana, Klara ^{[2
]}

Sen Gupta, Nalinava ^{[2
]}

Wragg, David ^{[2
]}

Tilset, Mats ^{[1
]}

机构：

[1] CTCC, Dept Chem, N-0315 Oslo, Norway

[2] Univ Oslo, Dept Chem, N-0315 Oslo, Norway

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2011年 / 76卷 / 08期

关键词：

ASYMMETRIC CYCLOPROPANATION; DIRHODIUM(II) COMPLEXES; ETHYL DIAZOACETATE; OLEFINS; CATALYST; DIASTEREOCONTROL; ENANTIOCONTROL; CONSTRUCTION; OPTIMIZATION; DERIVATIVES;

D O I：

10.1021/jo102140z

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The performance of recently reported highly cis-diastereoselective Rh(I) cyclopropanation catalysts has been significantly improved by a systematic study of different reaction parameters (catalyst activation, solvent, temperature, stoichiometry). The catalyst efficiency and diastereoselectivity were enhanced by changing the activating agent from AgOTf to NaBArf. With this new system, the Rh(I) catalyst was shown to be a highly efficient and cis-diastereoselective cyclopropanation catalyst in reactions between alpha-diazoacetates and a range of different alkenes and substituted derivatives. Particularly noteworthy is the remarkable reactivity and cis-diastereoselectivity displayed in the reactions between ethyl diazoacetate and cyclopentene, 2,5-dihydrofuran, and benzofuran, with yields up to 99% and cis-selectivities greater than 99%.

引用

页码：2465 / 2470

页数：6

共 45 条

[1] cis-Selective cyclopropanations using chiral 5,5-diaryl bis(oxazoline) catalysts [J].

Alexander, K ;

Cook, S ;

Gibson, CL .

TETRAHEDRON LETTERS, 2000, 41 (36) :7135-7138

[2] Cis-selective asymmetric cyclopropanation of olefins catalyzed by five-coordinate [RuCl(PNNP)]+ complexes [J].

Bachmann, S ;

Furler, M ;

Mezzetti, A .

ORGANOMETALLICS, 2001, 20 (10) :2102-2108

[3]

Bachmann S, 2001, HELV CHIM ACTA, V84, P3063, DOI 10.1002/1522-2675(20011017)84:10<3063::AID-HLCA3063>3.0.CO

[4]

2-R

[5] METAL-COMPLEXES OF WEAKLY COORDINATING ANIONS - PRECURSORS OF STRONG CATIONIC ORGANOMETALLIC LEWIS-ACIDS [J].

BECK, W ;

SUNKEL, K .

CHEMICAL REVIEWS, 1988, 88 (07) :1405-1421

[6] Chiral dicationic bis(aqua) complexes [Ru(OH2)2(PNNP)]2+:: The effect of double chloride abstraction on asymmetric cyclopropanation [J].

Bonaccorsi, C ;

Santoro, F ;

Gischig, S ;

Mezzetti, A .

ORGANOMETALLICS, 2006, 25 (08) :2002-2010

[7] Optimization or breakthrough?: The first highly cis- and enantioselective asymmetric cyclopropanation of 1-octene by "electronic and counterion" tuning of [RuCl(PNNP)]+ catalysts [J].

Bonaccorsi, C ;

Mezzetti, A .

ORGANOMETALLICS, 2005, 24 (21) :4953-4960

[8] Electronic tuning of the PNNP ligand for the asymmetric cyclopropanation of olefins catalysed by [RuCl(PNNP)] [J].

Bonaccorsi, C ;

Bachmann, S ;

Mezzetti, A .

TETRAHEDRON-ASYMMETRY, 2003, 14 (07) :845-854

[9] Highly efficient formation of halodiazoacetates and their use in stereoselective synthesis of halocyclopropanes [J].

Bonge, Hanne Therese ;

Pintea, Benjamin ;

Hansen, Tore .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2008, 6 (20) :3670-3672

[10] Metal-Catalyzed Olefin Cyclopropanation with Ethyl Diazoacetate: Control of the Diastereoselectivity [J].

Caballero, Ana ;

Prieto, Auxiliadora ;

Mar Diaz-Requejo, M. ;

Perez, Pedro J. .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2009, (09) :1137-1144

← 1 2 3 4 5 →