82297-57-2Relevant articles and documents
Palladium catalysed conversion of vinyl bromo allylic alcohols into vinylic carbonyl compounds and oxidation of secondary alcohols to ketones
Pitre, Sangceta V.,Vankar, Padma S.,Vankar, Yashwant D.
, p. 12291 - 12298 (2007/10/03)
A variety of vinyl bromo allylic alcohols are converted into the corresponding vinylic carbonyl compounds and secondary alcohols are oxidised into ketones upon treatment with palladium acetate in the presence of potassium carbonate under the typical Heck reaction conditions.
ENAMINE CHEMISTRY-XXV REDUCTION OF ENAMINONONES BY LiAlH4 AND NaBH4 SYNTHESIS OF α,β-UNSATURATED ALDEHYDES
Carlsson, S.,Lawesson, S.-O.
, p. 413 - 417 (2007/10/02)
Cyclohexanone, 2-methyl-cyclohexanone and 4-methyl-cyclohexanone, 1, were transformed into the enaminones 4a-4e by the following two routes: (A): Acylation of the enamines, 2, derived from 1 and secondary amines (pyrrolidine, morpholine and piperidine) by ethyl chloroformate, and (B): Condensation of 1 with diethyl oxalate, giving the β-ketoesters 3, followed by reaction with the secondary amines.Ethyl 2(-1-pyrrolidinyl)-1-cyclopentene-1-carboxylate. 4f, and methyl 3-(1-pyrrolidinyl)-2-buteonate, 4g, were prepared from ethyl 2-oxo-1-cyclopentanecarboxylate and ethyl 3-oxo-butanoate, respectively, by condensation with pyrrolidine.Reduction of 4a by LAH afforded 1-cyclohexen-1-carboxaldehyde, 5a, 1-cyclohexene-1-methanol, 6a, and 1-(1-cyclohexene-1-methyl)pyrrolidine, 7a, in yields depending on the molar ratio of LAH/4a.Reduction of 4f by LAH gave cyclopenten-1-methanol, 6b, 1-(1-cyclopentene-1-methyl)pyrrolidine, 7b, and ethyl-2(1-pyrrolidinyl)-1-cyclopentanecarboxylate, 8b.Compound 4g, when reduced with LAH, yielded methyl 3-(1-pyrrolidinyl) butanoate, 8c (main product) and 1-(2-butenyl)pyrrolidine, 7c (minor).Reduction of 4 by NaBH4 afforded exlusively the saturated β-aminoesters, 8, in high yields.The reductions with LAH and NaBH4 are rationalized in terms of the HSAB principle.
