通过亚乙基双（膦酸四乙酯）与1,3 - 二烯的狄尔斯 - 阿尔德环加成反应制备环己 - 3 - 烯 - 1,1 - 双（膦酸酯）的首次通用方法。

First general approach to cyclohex-3-ene-1,1-bis(phosphonates) by Diels-Alder cycloaddition of tetraethyl vinylidenebis(phosphonate) to 1,3-dienes.

作者信息

Ruzziconi Renzo, Ricci Giacomo, Gioiello Antimo, Couthon-Gourvès Hélène, Gourvès Jean-Philippe

机构信息

Dipartimento di Chimica, Università di Perugia, Via Elce di Sotto, 8 I-06123 Perugia, Italy.

出版信息

J Org Chem. 2003 Feb 7;68(3):736-42. doi: 10.1021/jo0205154.

DOI:10.1021/jo0205154

PMID:12558393

Abstract

Tetraethyl vinylidenebis(phosphonate) (VBP) reacts smoothly with substituted 1,3-dienes at 90-110 degrees C without solvent to give the corresponding cyclohex-3-ene-1,1-bis(phosphonates) in good yields (60-85%). With nonsymmetrically substituted dienes, mixtures of regioisomers are obtained, the regioisomeric ratio being exclusively controlled by electronic effects. Danishefsky's diene allows tetraethyl 4-oxocyclohex-2-ene-1,1-bis(phosphonate) to be obtained in an 81% overall yield after the acid-catalyzed hydrolysis of the Diels-Alder cycloadduct. With 2,3-dimethoxy-1,3-butadiene, a mixture of regioisomeric dimethoxycyclohexene-1,1-bis(phosphonates) is formed by the VBP-catalyzed isomerization of the normal Diels-Alder cycloadduct. The mixture converges into tetraethyl 3,4-dimethoxycyclohex-2-ene-1,1-bis(phosphonate) at prolonged reaction times.

摘要

亚乙基双（膦酸四乙酯）（VBP）在90 - 110℃无溶剂条件下与取代的1,3 - 二烯顺利反应，以良好产率（60 - 85%）生成相应的环己 - 3 - 烯 - 1,1 - 双（膦酸酯）。对于不对称取代的二烯，可得到区域异构体混合物，区域异构比完全由电子效应控制。经狄尔斯 - 阿尔德环加成物酸催化水解后，达尼谢夫斯基二烯可使4 - 氧代环己 - 2 - 烯 - 1,1 - 双（膦酸四乙酯）的总产率达到81%。对于2,3 - 二甲氧基 - 1,3 - 丁二烯，正常狄尔斯 - 阿尔德环加成物经VBP催化异构化形成区域异构的二甲氧基环己烯 - 1,1 - 双（膦酸酯）混合物。延长反应时间时，该混合物会转化为3,4 - 二甲氧基环己 - 2 - 烯 - 1,1 - 双（膦酸四乙酯）。