126754-20-9Relevant academic research and scientific papers
Enolate-Based Regioselective Anti-Beckmann C-C Bond Cleavage of Ketones
Jahn, Ullrich,Ma?ek, Tomá?
, p. 11608 - 11632 (2021/09/02)
The Baeyer-Villiger or Beckmann rearrangements are established methods for the cleavage of ketone derivatives under acidic conditions, proceeding for unsymmetrical precursors selectively at the more substituted site. However, the fragmentation regioselectivity cannot be switched and fragmentation at the less-substituted terminus is so far not possible. We report here that the reaction of ketone enolates with commercial alkyl nitrites provides a direct and regioselective way of fragmenting ketones into esters and oximes or ω-hydroxyimino esters, respectively. A comprehensive study of the scope of this reaction with respect to ketone classes and alkyl nitrites is presented. Control over the site of cleavage is gained through regioselective enolate formation by various bases. Oxidation of kinetic enolates of unsymmetrical ketones leads to the otherwise unavailable "anti-Beckmann"cleavage at the less-substituted side chain, while cleavage of thermodynamic enolates of the same ketones represents an alternative to the Baeyer-Villiger oxidation or the Beckmann rearrangement under basic conditions. The method is suited for the transformation of natural products and enables access to orthogonally reactive dicarbonyl compounds.
Convenient and high-yielding preparations of mono(5-carboxy-2-ethylpentyl) phthalate and its ring-deuterated isomer - The "third" major metabolite of bis(2-ethylhexyl) phthalate
Gilsing, Hans-Detlev,Angerer, Juergen,Prescher, Dietrich
, p. 795 - 801 (2007/10/03)
The synthesis of an oxidative major metabolite of bis(2-ethylhexyl) phthalate is described. The target molecule and its ring-deuterated isomer were obtained via acylation of the appropriate ω-hydroxy benzyl ester or the corresponding carboxylate with phthalic anhydride or phthalic anhydride-d 4. All transformation steps proceed with high yields. Springer-Verlag 2005.
CuX3Li2-catalysed Conjugate Addition of Dialkylmagnesium Reagents to α,β-Unsaturated Carbonyl Compounds
Reetz, Manfred T.,Kindler, Alois
, p. 2509 - 2510 (2007/10/02)
Copper salts of the type CuX3Li2 (X = halogen) catalyse the conjugate addition of dialkylmagnesium compounds to α,β-unsaturated carbonyl compounds in the presence or absence of Me3SiCl as an additive, the organomagnesium compounds being prepared from α-ol
The vinylogous anomeric effect in 3-alkyl-2-chlorocyclohexanone oximes and oxime ethers
Denmark,Dappen,Sear,Jacobs
, p. 3466 - 3474 (2007/10/02)
A series of trans-3-alkyl-2-chlorocyclohexanones, 2(methyl, ethyl, isopropyl, and tert-butyl), have been prepared and shown to exist predominantly in the diequatorial chair conformation except the tert-butyl derivative which prefers a twist-boat. Formatio
