期刊
GREEN CHEMISTRY
卷 11, 期 12, 页码 1992-2000出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/b916117a
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资金
- Ministerio de Educacion y Ciencia (MEC) of Spain [CTQ2006-08485/BQU]
- Consolider Ingenio 2010 [CSD2007-00006]
- Gobierno del Principado de Asturias [IB08-036]
- European Social Fund
- Ramon y Cajal
The hexamethylbenzene-ruthenium(II) dimer [{RuCl(mu-Cl)(eta(6)-C6Me6)}(2)] 1 and the mononuclear bis(allyl)-ruthenium(IV) complex [RuCl2(eta(3):eta(2):eta(3)-C12H18)](2), associated with base and a hydrogen donor, were found to be active catalysts for the selective reduction of the C=C bond of allylic alcohols both in organic and aqueous media. The process, which proceeds in a one-pot manner, involves a sequence of two independent reactions: (i) the initial redox-isomerization of the allylic alcohol, and (ii) subsequent transfer hydrogenation of the resulting carbonyl compound. The highly efficient transformation reported herein represents, not only an illustrative example of auto-tandem catalysis, but also an appealing alternative to the classical transition-metal catalyzed C=C hydrogenations of allylic alcohols. The process has been successfully applied to aromatic as well as aliphatic substrates affording the corresponding saturated alcohols in 45-100% yields after 1.5-24 h. The best performances were reached using (i) 1-5 mol% of 1 or 2, 2-10 mol% of Cs2CO3, and propan-2-ol or (ii) 1-5 mol% of 1 or 2, 10-15 equivalents of NaO2CH, and water. The catalytic efficiency is strongly related to the structure of the allylic alcohol employed. Thus, in propan-2-ol, the reaction rate essentially depends on the steric requirement around the C=C bond, therefore decreasing with the increasing number of substituents. On other hand, in water the transformation is favoured for primary allylic alcohols vs. secondary ones.
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