Neighboring group participation in a regio- and stereoselective chlorination of a bicyclo[2.2.2]octanone

被引：9

作者：

Almqvist, F ^{[1
]}

Frejd, T ^{[1
]}

机构：

[1] LUND UNIV,DEPT CHEM,S-22100 LUND,SWEDEN

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1996年 / 61卷 / 20期

关键词：

D O I：

10.1021/jo9607370

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The zinc chloride-mediated acetylation of the optically active silyl enol ether 2a gave the beta-diketone 3a (48%) together with the regio- and stereoselectively chlorinated compound 4 (27%). The yield of 4 increased to 70% by starting from the O-acetyl derivative 2c. The chlorination most likely occurs via neighboring group participation by the endo acetoxy group.

引用

收藏

页码：6947 / 6951

页数：5

相关论文

共 27 条

[1] Synthesis of optically active endo,endo bicyclo[2.2.2]octane-2,5-diol, bicyclo[2.2.2]octane-2,5-dione, and related compounds [J].

Almqvist, F ;

Ekman, N ;

Frejd, T .

JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (11) :3794-3798

[2] OPTICALLY-ACTIVE BICYCLO[2.2.2]OCTANE DERIVATIVES - SYNTHESIS OF (1S,4R,6R)-6-HYDROXYBICYCLO[2.2.2]OCTAN-2-ONE FROM ITS ENANTIOMER [J].

ALMQVIST, F ;

FREJD, T .

TETRAHEDRON-ASYMMETRY, 1995, 6 (04) :957-960

[3]

ALMQVIST F, IN PRESS

[4]

ALMQVIST F, 1993, SYNTHETIC COMMUN, P1499

[5] SYNTHESIS OF 2 USEFUL, ENANTIOMERICALLY PURE DERIVATIVES OF (S)-4-HYDROXY-2-CYCLOHEXENONE [J].

AUDIA, JE ;

BOISVERT, L ;

PATTEN, AD ;

VILLALOBOS, A ;

DANISHEFSKY, SJ .

JOURNAL OF ORGANIC CHEMISTRY, 1989, 54 (15) :3738-3740

[6] EXO-6-BENZYL-EXO-2-(META-HYDROXYPHENYL)-1-DIMETHYLAMINOMETHYLBICYCLO[2.2.2.]OCTANE - A NONPEPTIDE MIMIC OF ENKEPHALINS [J].

BELANGER, PC ;

DUFRESNE, C .

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1986, 64 (08) :1514-1520

[7] REACTION OF FECL3 WITH 7-CHLORO-1-SILYLOXYBICYCLO[4-1-O]HEPTANES - A WAY TO 2-(1-CHLOROALKYLIDENE)CYCLOHEXANONES [J].

BLANCO, L ;

MANSOURI, A .

TETRAHEDRON LETTERS, 1988, 29 (26) :3239-3242

[8] PREPARATION AND REACTIONS OF BETA-CHLORO-ALPHA,BETA-UNSATURATED KETONES [J].

CLARK, RD ;

HEATHCOCK, CH .

JOURNAL OF ORGANIC CHEMISTRY, 1976, 41 (04) :636-643

[9]

Colvin E. W., 1988, SILICON REAGENTS ORG

[10] THE TOTAL SYNTHESIS OF (+/-)-TRICHOSTATIN-A - SOME OBSERVATIONS ON THE ACYLATION AND ALKYLATION OF SILYL ENOL ETHERS, SILYL DIENOL ETHERS AND A SILYL TRIENOL ETHER [J].

FLEMING, I ;

IQBAL, J ;

KREBS, EP .

TETRAHEDRON, 1983, 39 (06) :841-846