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水相中N-烯丙基酰胺和内酰胺催化脱保护的高效串联过程:双(烯丙基)-钌(IV)催化剂[Ru(η3:η2:η3-C12H18)Cl2]和[{Ru(η3:η3-C10H16)(μ-Cl)Cl}2]的新应用

Efficient tandem process for the catalytic deprotection of N-allyl amides and lactams in aqueous media: a novel application of the bis(allyl)-ruthenium(IV) catalysts [Ru(eta3:eta2:eta3-C12H18)Cl2] and [{Ru(eta3:eta3-C10H16)(micro-Cl)Cl}2].

作者信息

Cadierno Victorio, Gimeno José, Nebra Noel

机构信息

Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Química Organometálica, Enrique Moles (Unidad Asociada al CSIC), Universidad de Oviedo, Julián Clavería 8, E-33006 Oviedo, Spain.

出版信息

Chemistry. 2007;13(23):6590-4. doi: 10.1002/chem.200700477.

DOI:10.1002/chem.200700477
PMID:17516612
Abstract

An operationally simple and highly efficient methodology for the removal of the allyl protecting group in amides and lactams has been developed by using the commercially available bis(allyl)-ruthenium(IV) catalysts [Ru(eta(3):eta(2):eta(3)-C(12)H(18))Cl(2)] (C(12)H(18)=dodeca-2,6,10-triene-1,12-diyl) and [{Ru(eta(3):eta(3)-C(10)H(16))(micro-Cl)Cl}(2)] (C(10)H(16)=2,7-dimethylocta-2,6-diene-1,8-diyl). The tandem process, which takes place in aqueous media and proceeds in a one-pot manner, involves the initial isomerization of the C=C bond of the allyl unit and subsequent oxidative cleavage of the resulting enamide.

摘要

通过使用市售的双(烯丙基)-钌(IV)催化剂[Ru(η(3):η(2):η(3)-C₁₂H₁₈)Cl₂](C₁₂H₁₈ = 十二碳-2,6,10-三烯-1,12-二基)和[{Ru(η(3):η(3)-C₁₀H₁₆)(μ-Cl)Cl}₂](C₁₀H₁₆ = 2,7-二甲基辛-2,6-二烯-1,8-二基),已经开发出一种操作简单且高效的方法,用于去除酰胺和内酰胺中的烯丙基保护基团。该串联过程在水性介质中以一锅法进行,涉及烯丙基单元的C=C键的初始异构化以及所得烯酰胺的后续氧化裂解。

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