STEREOSELECTIVE FORMATION OF 3 CARBON-CARBON BONDS BY CASCADE REACTION WITH ENOLATE ANION - SYNTHESIS OF TRICYCLO[6.2.2.0(1,6)] DODECANE AND TRICYCLO[5.3.1.0(3,8)]UNDECANE DERIVATIVES

被引：27

作者：

IHARA, M ^{[1
]}

MAKITA, K ^{[1
]}

TOKUNAGA, Y ^{[1
]}

FUKUMOTO, K ^{[1
]}

机构：

[1] TOHOKU UNIV,INST PHARMACEUT,SENDAI 98077,MIYAGI,JAPAN

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1994年 / 59卷 / 20期

关键词：

D O I：

10.1021/jo00099a034

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Reaction of 6-[5(E)-6-(methoxycarbonyl)hex-5-enyl]-2-cyclohexen-1-one (1) with LHMDS, followed by one-pot treatment with CH2O, resulted in a cascade Michael-Michael-aldol reaction, producing hydroxymethylated tricyclo[6.2.2.0(1,6)]dodecane 3. The methylated tricyclo[5.3.1.0(3,8)]undecane 21 was obtained by a Michael-Michael-substitution reaction, performed by reaction of 5-[4(E)-5(methoxycarbonyl)pent-4-enyl]-2-methyl-2-cyclohexen-1-one (11) with LHMDS and one-pot treatment with MeI in the presence of HMPA. Michael-Michael-aldol reactions of 11 were also carried out with LHMDS followed by several aldehydes to provide tricyclo[5.3.1.0(3,8)]undecane derivatives 22, 23, and 24, respectively. The importance of intramolecular coordination wit h lithium for the double Michael reaction was supported by an experiment utilizing the corresponding (Z)-isomer 13.

引用

页码：6008 / 6013

页数：6

共 39 条

[1] BICYCLOANNULATION .5. VINYLPHOSPHONIUM BICYCLOANNULATION OF CYCLOHEXENONES AND ITS USE IN A STEREOSELECTIVE SYNTHESIS OF TRACHYLOBAN-19-OIC ACID [J].