Palladium-catalyzed selective activation of allyl alcohols as allyl cations, allyl anions, and zwitterionic trimethylenemethanes

被引：16

作者：

Tamaru, Yoshinao ^{[1
]}

Kimura, Masanari ^{[1
]}

机构：

[1] Nagasaki Univ, Fac Engn, Dept Appl Chem, Nagasaki 8528521, Japan

来源：

PURE AND APPLIED CHEMISTRY | 2008年 / 80卷 / 05期

关键词：

allyl alcohols; allyl anions; allyl cations; catalysis; palladium; triethylborane; trimethylenemethane; umpolung;

D O I：

10.1351/pac200880050979

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Pd-Et3B catalytic system promotes the generation of allyl cations, allyl anions, and zwitterionic trimethylenemethane species from the corresponding allylic alcohols. Allyl cations react with a wide variety of nucleophiles, e.g., amines, active methylene compounds, 1,3,5-trihydroxybenzene, indoles, aldehydes (at the alpha-position). The reaction is extended to dehydrative Grob fragmentation of 1,3-diols. Allyl anions react with aldimines to give homo-allyl amines. Zwitterionic trimethylenemethane, generated from 2-methylene-1,3 -propanediol, reacts with aldehydes and aldimines to provide 3-methylenecyclopentanols and 3-methylenepyrrolidines, respectively. Vinyl epoxide can be utilized as a synthetic equivalent of 3-butenyl 2-anion-1-cation.

引用

页码：979 / 991

页数：13

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