Titanocene-Promoted Eliminations on Epoxy Alcohols and Epoxy Esters

Titanocene-Promoted Eliminations on Epoxy Alcohols and Epoxy Esters
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DOI:
10.1002/ejoc.200901222
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发表时间:
2010-02-01
影响因子:
2.8
通讯作者:
Rubio Gonzalez, Rosa
Rubio Gonzalez, Rosa
中科院分区:
化学3区
文献类型:
--
作者:
Fernandez-Mateos, Alfonso;Encinas Madrazo, Soledad;Rubio Gonzalez, Rosa

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研究了Cp2TiCl促进的一系列2,3-环氧醇与相应的甲酸酯、乙酸酯和苯甲酸酯的反应。环氧衍生物反应的不同结果已经从机械偏向过程的角度进行了合理化。均解环氧烷裂解后,发现了四种主要的反应类型:脱羟基、脱羧基、脱氢和脱氧。反应产物随取代方式的不同而不同。这些消除的激进性质得到了证明。
The reaction of a series of 2,3-epoxy alcohols and the corresponding formates, acetates, and benzoates promoted by Cp2TiCl has been studied. The different outcome of the reaction of epoxy derivatives has been rationalized in terms of mechanistically biased processes. After homolytic oxirane cleavage, four main types of reaction were found: dehydroxylation, decarboxylation, dehydrogenation, and deoxygenation. The reaction products varied according to the substitution pattern. The radical nature of these eliminations is demonstrated.