Reactions of substituted (1,3-butadiene-1,4-diyl)magnesium, 1,4-bis(bromomagnesio)butadienes and 1,4-dilithiobutadienes with ketones, aldehydes and PhNO to yield cyclopentadiene derivatives and N-Ph pyrroles by cyclodialkenylation

被引:40
作者
Fang, HY
Li, GT
Mao, GL
Xi, ZF [1 ]
机构
[1] Peking Univ, Coll Chem, Minist Educ, Key Lab Bioorgan Chem & Mol Engn, Beijing 100871, Peoples R China
[2] Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organomet Chem, Shanghai 200032, Peoples R China
关键词
carbonyl compounds; cyclopentadienes; heterocycles; lithiation; pyrroles;
D O I
10.1002/chem.200400025
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
1,4-Dilithiobutadiene derivatives 1, 1,4-bis(bromomagnesio)butadiene derivatives 2 and metallacyclic (1,3-butadiene-1,4-diyl)magnesium reagents 3 were prepared and their reactions with ketones, aldehydes, and PhNO were investigated. Multiply substituted cyclopentadienes and N-Ph pyrroles were formed by unprecedented reaction conditions. The carbonyl group of aldehydes and ketones was deoxygenated during the reaction and behaved formally as a one-carbon unit; the N=O moiety of PhNO was cleaved to afford N-Ph pyrrole derivatives. Furthermore, different reactivities among these three types of reagents 1, 2 and 3 were revealed. The 1,4-dilithium reagents 1 readily reacted with both aldehydes and ketones; the 1,4-dimagnesium reagents 2 reacted with aldehydes, but not ketones; the metallacyclopentadiene reagents of magnesium. 3 showed higher reactivity and did react with ketones.
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页码:3444 / 3450
页数:7
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