- Oxidative Cleavage of Alkenes by O2with a Non-Heme Manganese Catalyst
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The oxidative cleavage of C═C double bonds with molecular oxygen to produce carbonyl compounds is an important transformation in chemical and pharmaceutical synthesis. In nature, enzymes containing the first-row transition metals, particularly heme and non-heme iron-dependent enzymes, readily activate O2 and oxidatively cleave C═C bonds with exquisite precision under ambient conditions. The reaction remains challenging for synthetic chemists, however. There are only a small number of known synthetic metal catalysts that allow for the oxidative cleavage of alkenes at an atmospheric pressure of O2, with very few known to catalyze the cleavage of nonactivated alkenes. In this work, we describe a light-driven, Mn-catalyzed protocol for the selective oxidation of alkenes to carbonyls under 1 atm of O2. For the first time, aromatic as well as various nonactivated aliphatic alkenes could be oxidized to afford ketones and aldehydes under clean, mild conditions with a first row, biorelevant metal catalyst. Moreover, the protocol shows a very good functional group tolerance. Mechanistic investigation suggests that Mn-oxo species, including an asymmetric, mixed-valent bis(μ-oxo)-Mn(III,IV) complex, are involved in the oxidation, and the solvent methanol participates in O2 activation that leads to the formation of the oxo species.
- Bennett, Elliot L.,Brookfield, Adam,Guan, Renpeng,Huang, Zhiliang,Mcinnes, Eric J. L.,Robertson, Craig M.,Shanmugam, Muralidharan,Xiao, Jianliang
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supporting information
p. 10005 - 10013
(2021/07/19)
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- Transformations of peroxide olefin ozonolysis products in methanol in the presence of water
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Transformations of peroxide products of ozonolysis of various olefins with different degrees of substitution at the double bond by the action of hydroxylamine and semicarbazide hydrochloride in methanol in the presence of water as co-solvent were studied.
- Ishmuratov,Legostaeva,Garifullina,Botsman,Muslukhov,Tolstikov
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p. 1415 - 1419
(2014/01/06)
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- Photo-cleavage of carbon-carbon bond of α-iodocycloalkanones giving ω,ω-dialkoxyalkanoic ester in alcohol
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The irradiation at λ > 300 nm of α-iodocycloalkanones with a high- pressure mercury lamp in alcohols containing a small amount of water afforded the corresponding ω,ω-dialkoxyalkanoic ester (65-88%) by photochemical cleavage of the C(I)-C=O bond at room temperature. In the case of a commercial fluorescent lamp as the irradiating light source, photochemical ring-opening products were also obtained. The irradiation of 2α-iodo-5α- and 4β-iodo-5β-cholestan-3-ones in methanol gave methyl 2,2-dimethoxy-2,3- seco-5α-cholestan-3-oate and methyl 4,4-dimethoxy-3,4-seco-5β-cholestan-3- oate in 78 and 62% yields, respectively. The photochemical behavior of the cleavage reaction of α-iodocycloalkanones is also discussed on the basis of 2-hydroxycycloalkanone as an intermediate.
- Ji, Shun-Jun,Horiuchi, C. Akira
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p. 1645 - 1652
(2007/10/03)
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