Rh-catalyzed formation of dioxolanes from α-alkyl diazoesters:: Diastereoselective cycloadditions of carbonyl ylides with selectivity over β-hydride elimination

被引：46

作者：

DeAngelis, Andrew ^{[1
]}

Panne, Patricia ^{[1
]}

Yap, Glenn P. A. ^{[1
]}

Fox, Joseph M. ^{[1
]}

机构：

[1] Univ Delaware, Dept Chem & Biochem, Brown Labs, Newark, DE 19716 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2008年 / 73卷 / 04期

关键词：

D O I：

10.1021/jo702308f

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Described here is a diastereoselective Rh-catalyzed method for the preparation of dioxolanes from alpha-alkyl-alpha-diazoesters. This represents the first general method for generating carbonyl ylides from alpha-diazoesters that possess beta-hydrogens, as such diazo compounds typically give rise to alkenes via beta-hydride elimination. Subsequent cycloaddition with aromatic aldehydes gives tetrasubstituted dioxolanes with unusually high diastereoselectivity. A model is set forth to explain the diastereoselectivity of the cycloaddition.

引用

页码：1435 / 1439

页数：5

共 35 条

[1] SYNTHESIS OF AN ALPHA-(AMINOOXY)ARYLACETIC ESTER BY THE REACTION OF AN ALPHA-DIAZO ESTER WITH N-HYDROXYPHTHALIMIDE [J].

ACE, KW ;

HUSSAIN, N ;

LATHBURY, DC ;

MORGAN, DO .

TETRAHEDRON LETTERS, 1995, 36 (44) :8141-8144

[2] RHODIUM (II) CATALYZED-REACTIONS OF DIAZO-CARBONYL COMPOUNDS [J].

ADAMS, J ;

SPERO, DM .

TETRAHEDRON, 1991, 47 (10-11) :1765-1808

[3] TRANSITION-METAL-CATALYZED DECOMPOSITION OF DIAZO(TRIALKYLSILYL)-ACETATES - INTERMOLECULAR FORMATION AND TRAPPING OF CARBONYL YLIDES [J].

ALT, M ;

MAAS, G .

TETRAHEDRON, 1994, 50 (25) :7435-7444

[4] COMPETING O-H INSERTION AND BETA-ELIMINATION IN RHODIUM CARBENOID REACTIONS - SYNTHESIS OF 2-ALKOXY-3-ARYLPROPANOATES [J].

COX, GG ;

HAIGH, D ;

HINDLEY, RM ;

MILLER, DJ ;

MOODY, CJ .

TETRAHEDRON LETTERS, 1994, 35 (19) :3139-3142

[5] Stereoselective synthesis of epoxides by reaction of donor/acceptor-substituted carbenoids with α,β-unsaturated aldehydes [J].

Davies, HML ;

DeMeese, J .

TETRAHEDRON LETTERS, 2001, 42 (39) :6803-6805

[6]

Doyle M. P., 1998, Modern Catalytic Methods for Organic Synthesis with Diazo Compounds: From Cyclopropanes to Ylides

[7] Recent advances in asymmetric catalytic metal carbene transformations [J].

Doyle, MP ;

Forbes, DC .

CHEMICAL REVIEWS, 1998, 98 (02) :911-935

[8] Epoxides and aziridines from diazoacetates via ylide intermediates [J].

Doyle, MP ;

Hu, WH ;

Timmons, DJ .

ORGANIC LETTERS, 2001, 3 (06) :933-935

[9] Stereocontrol in intermolecular dirhodium(II)-catalyzed carbonyl ylide formation and reactions. Dioxolanes and dihydrofurans [J].

Doyle, MP ;

Forbes, DC ;

Protopopova, MN ;

Stanley, SA ;

Vasbinder, MM ;

Xavier, KR .

JOURNAL OF ORGANIC CHEMISTRY, 1997, 62 (21) :7210-7215

[10] EXCEPTIONALLY HIGH TRANS (ANTI) STEREOSELECTIVITY IN CATALYTIC CYCLOPROPANATION REACTIONS [J].

DOYLE, MP ;

BAGHERI, V ;

WANDLESS, TJ ;

HARN, NK ;

BRINKER, DA ;

EAGLE, CT ;

LOH, KL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (05) :1906-1912

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