摘要
联烯酸酯是近年来研究较多的一类重要的缺电子联烯,具有丰富的化学反应.本文着重总结了近年来在叔膦参与下(催化或化学计量方式)联烯酸酯与醛的新反应,包括2,3-丁二烯酸酯与醛的成环反应、γ-取代联烯酸酯与醛的[3+2]环加成反应和烯化反应、α-取代联烯酸酯与醛的Vinylogous Wittig反应以及环丙烷化反应,并从反应机理的角度,探讨了联烯酸酯与亲电试剂活化烯、亚胺和醛在反应性上的差异.在这些重要的化学转化中,叔膦的特殊性质如亲核性与夺氧能力起了关键的作用.
Allenoates as an important class of electron-deficient allenes possess diverse reactivities,which have been extensively investigated in recent years.This review primarily summarizes recent advances in the tertiary phosphine-mediated（catalytic or stoichiometric） reactions between allenoates and aldehydes,which include annulations of 2,3-butadienoates with aldehydes,the [3＋2] cycloaddition reaction and olefination between γ-substituted allenoates and aldehydes,vinylogous Wittig reaction and cyclopropanation of α-substituted allenoates with aldehydes,respectively.In light of those already accepted plausible mechanisms,rationalized are the differences in the reactivities of allenoates with different electrophiles including activated olefins,imines and aldehydes.In the reported chemical transformations,tertiary phosphines with inherent properties like nucleophilicity and deoxygenating ability play critical roles.
出处
《中国科学：化学》
CAS
CSCD
北大核心
2010年第7期856-868,共13页
SCIENTIA SINICA Chimica
基金
国家自然科学基金(20672057
20872063)的资助
关键词
叔膦
联烯
醛
催化
合成反应
tertiary phosphine
allene
aldehyde
catalysis
synthetic reaction
