IONIC IODOCARBOCYCLIZATION REACTIONS OF 4-ALKENYLMALONATE AND 4-ALKYNYLMALONATE DERIVATIVES

被引：54

作者：

KITAGAWA, O ^{[1
]}

INOUE, T ^{[1
]}

HIRANO, K ^{[1
]}

TAGUCHI, T ^{[1
]}

机构：

[1] TOKYO COLL PHARM,1432-1 HORINOUCHI,HACHIOJI,TOKYO 19203,JAPAN

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1993年 / 58卷 / 11期

关键词：

D O I：

10.1021/jo00063a033

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The cyclization reactions of dimethyl 4-alkenylmalonate derivatives la-d in the presence Of 12 and Ti(Ot-Bu)4 proceed in a highly regio- and stereocontrolled manner (5-exo cyclization and trans addition) to give (iodoalkyl)cyclopentane derivatives 2 or bicyclic lactones 3 through the displacement of the iodide of 2 by an ester group. Iodocarbocyclization reactions of dimethyl [(cycloalkenyl)alkyl]malonates 1g-i or dimethyl [(methylenecycloalkyl)alkyl]malonates 1j and 1k proceed regio- and stereoselectively to give fused ring compounds or spiro compounds, respectively, as single isomers. Similar reactions of 4-alkynyl derivatives 5 give preferentially E-iodomethylene cyclopentane derivatives 6. An ionic mechanism rather than a radical mechanism is suggested on the basis of the regioselectivity and stereospecificity of the above reactions.

引用

页码：3106 / 3112

页数：7

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