Dirhodium(II) tetrakis[N-tetrafluorophthaloyl-(S)-tert-leucinate]:: an exceptionally effective Rh(II) catalyst for enantiotopically selective aromatic C-H insertions of diazo ketoesters

被引：73

作者：

Tsutsui, H ^{[1
]}

Yamaguchi, Y ^{[1
]}

Kitagaki, S ^{[1
]}

Nakamura, S ^{[1
]}

Anada, M ^{[1
]}

Hashimoto, S ^{[1
]}

机构：

[1] Hokkaido Univ, Grad Sch Pharmaceut Sci, Sapporo, Hokkaido 0600812, Japan

来源：

TETRAHEDRON-ASYMMETRY | 2003年 / 14卷 / 07期

关键词：

D O I：

10.1016/S0957-4166(03)00075-2

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Dirhodium(II) tetrakis[N-tetrafluorophthaloyl-(S)-tert-leucinate], Rh-2[(S)-TFPTTL](4), in which the phthalimido hydrogen atoms of the parent dirhodium(II) complex are substituted by fluorine atoms, dramatically enhances the reactivity and enantioselectivity (up to 97% ee) in intramolecular aromatic C-H insertion reactions of methyl 4-alkyl-2-diazo-4,4-diphenyl-3-oxopropionates. Catalysis with the use of 0.001 mol% of Rh-2[(S)-TFPTTL](4) has achieved the highest turnover number (up to 98,000 with the methyl substituent) ever recorded for chiral dirhodium(II) complex-catalyzed carbene transformations, without compromising the yield or enantioselectivity of the process. (C) 2003 Elsevier Science Ltd. All rights reserved.

引用

页码：817 / 821

页数：5

共 73 条

[1] CHROMIUM CATALYZED ASYMMETRIC ALKENE EPOXIDATION - GREATER SELECTIVITY FOR AN E-ALKENE VERSUS ITS Z-ISOMER [J].

BOUSQUET, C ;

GILHEANY, DG .

TETRAHEDRON LETTERS, 1995, 36 (42) :7739-7742

[2] RHODIUM(II)2,4,6-TRIARYLBENZOATES - IMPROVED CATALYSTS FOR THE SYN CYCLOPROPANATION OF Z-OLEFINS [J].

CALLOT, HJ ;

METZ, F .

TETRAHEDRON, 1985, 41 (20) :4495-4501

[3] CHEMOSELECTIVITY OF RHODIUM CARBENOIDS - A COMPARISON OF THE SELECTIVITY FOR O-H INSERTION REACTIONS OR CARBONYL YLIDE FORMATION VERSUS ALIPHATIC AND AROMATIC C-H INSERTION AND CYCLOPROPANATION [J].

COX, GG ;

MOODY, CJ ;

AUSTIN, DJ ;

PADWA, A .

TETRAHEDRON, 1993, 49 (23) :5109-5126

[4]

Davies H. M. L., 1997, ALDRICHIM ACTA, V30, P107

[5] Stereoselectivity of methyl aryldiazoacetate cyclopropanations of 1,1-diarylethylene. Asymmetric synthesis of a cyclopropyl analogue of tamoxifen [J].

Davies, HML ;

Nagashima, T ;

Klino, JL .

ORGANIC LETTERS, 2000, 2 (06) :823-826

[6] Catalytic asymmetric C-H activation of alkanes and tetrahydrofuran [J].

Davies, HML ;

Hansen, T ;

Churchill, MR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (13) :3063-3070

[7] Enantioselective synthesis of fused cycloheptadienes by a tandem intramolecular cyclopropanation/cope rearrangement sequence [J].

Davies, HML ;

Doan, BD .

JOURNAL OF ORGANIC CHEMISTRY, 1999, 64 (23) :8501-8508

[8] 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

[9] Asymmetric intramolecular C-H insertions of aryldiazoacetates [J].

Davies, HML ;

Grazini, MVA ;

Aouad, E .

ORGANIC LETTERS, 2001, 3 (10) :1475-1477

[10]

Davies HML, 1998, CURR ORG CHEM, V2, P463

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