27970-80-5Relevant articles and documents
Manganese-catalyzed selective oxidation of aliphatic C-H groups and secondary alcohols to ketones with hydrogen peroxide
Dong, Jia Jia,Unjaroen, Duenpen,Mecozzi, Francesco,Harvey, Emma C.,Saisaha, Pattama,Pijper, Dirk,De Boer, Johannes W.,Alsters, Paul,Feringa, Ben L.,Browne, Wesley R.
, p. 1774 - 1778 (2013/10/21)
An efficient and simple method for selective oxidation of secondary alcohols and oxidation of alkanes to ketones is reported. An in situ prepared catalyst is employed based on manganese(II) salts, pyridine-2-carboxylic acid, and butanedione, which provides good-to-excellent conversions and yields with high turnover numbers (up to 10 000) with H2O2 as oxidant at ambient temperatures. In substrates bearing multiple alcohol groups, secondary alcohols are converted to ketones selectively and, in general, benzyl C-H oxidation proceeds in preference to aliphatic C-H oxidation. Manganeasy! MnII, picolinic acid, and butanedione make a smart mix for oxidation of secondary alcohols and alkanes and especially benzylic groups to ketones at room temperature with near stoichiometric amounts of hydrogen peroxide, low catalyst loadings, and high turn-over numbers. Copyright
RuHCl(CO)(PPh3)3-catalyzed reductive dimerization of α,β-unsaturated aldehydes leading to α-hydroxymethyl ketones
Doi, Takashi,Fukuyama, Takahide,Minamino, Satoshi,Ryu, Ilhyong
, p. 3013 - 3016 (2008/02/12)
The reductive dimerization α,β-unsaturated aldehydes to give saturated ketones was achieved using RuHCl(CO)(PPh3)3 as a catalyst in the presence of secondary alcohols as hydrogen source. The reaction is likely to proceed via the hydroruthenation of α,β-unsaturated aldehydes followed by aldol reaction of the resultant ruthenium enolates with α,β-unsaturated aldehydes to give unsaturated α-hydroxymethyl ketones, which undergo transfer hydrogenation to give α-hydroxymethyl ketones. Georg Thieme Verlag Stuttgart.
Aqueous biphasic oxidation: A water-soluble polyoxometalate catalyst for selective oxidation of various functional groups with hydrogen peroxide
Sloboda-Rozner, Dorit,Witte, Peter,Alsters, Paul L.,Neumann, Ronny
, p. 339 - 345 (2007/10/03)
A "sandwich" type polyoxometalate, Na12[(WZn 3(H2O)2][(ZnW9O34) 2], was used as an oxidation catalyst in aqueous biphasic reaction media to effect oxidation of alcohols, diols, pyridine derivatives, amines and aniline derivatives with hydrogen peroxide. The catalyst was shown by 183W NMR to be stable in aqueous solutions in the presence of H 2O2 and showed only minimal non-productive decomposition of the oxidant. Secondary alcohols were selectively oxidized to ketones, while primary alcohols tended to be oxidized to the corresponding carboxylic acids, although secondary alcohols were selectively oxidized in the presence of primary alcohols. Vicinal diols yielded carbon-carbon bond cleavage products in very high yields. Pyridine derivatives were oxidized to the respective TV-oxides, but strongly electron-withdrawing moieties inhibited the oxidation reaction. Primary amines were oxidized to the oximes, but significantly hydrolyzed in situ. Aniline derivatives were oxidized to the corresponding azoxy or nitro products depending on the substitution pattern in the aromatic ring. Catalyst recovery and recycle was demonstrated.
