STEREOCHEMICAL CONTROL IN THE ESTER ENOLATE CLAISEN REARRANGEMENT .1. STEREOSELECTIVITY IN SILYL KETENE ACETAL FORMATION

被引：285

作者：

IRELAND, RE

WIPF, P

ARMSTRONG, JD

机构：

[1] Department of Chemistry, University of Virginia, Charlottesville, Virginia 22901, McCormick Rd.

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1991年 / 56卷 / 02期

关键词：

D O I：

10.1021/jo00002a030

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Methods for the stereoselective deprotonation and silylation of esters were systematically investigated. A kinetically controlled enolization in combination with a kinetic resolution process accounts for the selective formation of (E)- and (Z)-silyl ketene acetals in THF and THF/dipolar solvent systems with bases such as LDA, LHMDS, and KHMDS. A thermodynamic equilibration mechanism seems to be of minor significance with ester enolates. Improved reaction conditions were exemplified in a highly stereoselective Claisen rearrangement in THF/45% DMPU.

引用

收藏

页码：650 / 657

页数：8

相关论文

共 64 条

[31] CLAISEN REARRANGEMENT OF ALLYL ESTERS [J].

IRELAND, RE ;

MUELLER, RH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (16) :5897-&

[32] ESTER ENOLATE CLAISEN REARRANGEMENT - STEREOCHEMICAL CONTROL THROUGH STEREOSELECTIVE ENOLATE FORMATION [J].

IRELAND, RE ;

MUELLER, RH ;

WILLARD, AK .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1976, 98 (10) :2868-2877

[33] THE TOTAL SYNTHESIS OF IONOPHORE ANTIBIOTICS - A CONVERGENT SYNTHESIS OF LASALOCID-A (X537A) [J].

IRELAND, RE ;

ANDERSON, RC ;

BADOUD, R ;

FITZSIMMONS, BJ ;

MCGARVEY, GJ ;

THAISRIVONGS, S ;

WILCOX, CS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (07) :1988-2006

[34] GENERATION OF C-GLYCOSIDES THROUGH THE ENOLATE CLAISEN REARRANGEMENT [J].

IRELAND, RE ;

WILCOX, CS ;

THAISRIVONGS, S ;

VANIER, NR .

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1979, 57 (13) :1743-1745

[35] APPROACH TO THE TOTAL SYNTHESIS OF CHLOROTHRICOLIDE - SYNTHESIS OF (+/-)-19,20-DIHYDRO-24-O-METHYLCHLOROTHRICOLIDE, METHYL-ESTER, ETHYL CARBONATE [J].

IRELAND, RE ;

VARNEY, MD .

JOURNAL OF ORGANIC CHEMISTRY, 1986, 51 (05) :635-648

[36] SYNTHESIS OF CHIRAL SUBUNITS FOR MACROLIDE SYNTHESIS - THE PRELOG-DJERASSI LACTONE AND DERIVATIVES [J].

IRELAND, RE ;

DAUB, JP .

JOURNAL OF ORGANIC CHEMISTRY, 1981, 46 (03) :479-485

[37] TOTAL SYNTHESIS OF LASALOCID-A (X537A) [J].

IRELAND, RE ;

THAISRIVONGS, S ;

WILCOX, CS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (03) :1155-1157

[38]

IRELAND RE, 1975, TETRAHEDRON LETT, V46, P3975

[39]

IRELAND RE, UNPUB

[40] ENOLATE CLAISEN REARRANGEMENT OF GLYCOLATE ESTERS [J].

KALLMERTEN, J ;

GOULD, TJ .

TETRAHEDRON LETTERS, 1983, 24 (47) :5177-5180

← 1 2 3 4 5 6 7 →