Synthesis of asymmetric peroxides: transition metal (Cu, Fe, Mn, Co) catalyzed peroxidation of beta-dicarbonyl compounds with tert-butyl hydroperoxide.
The transition metal (Cu, Fe, Mn, Co) catalyzed peroxidation of beta-dicarbonyl compounds at the alpha position by tert-butyl hydroperoxide was discovered. A selective, experimentally convenient, and gram-scale method was developed for the synthesis of alpha-peroxidated derivatives of beta-diketones, beta-keto esters, and diethyl malonate. Virtually stoichiometric (2-3/1) molar ratios of tert-butyl hydroperoxide and a dicarbonyl compound were used in the reactions with beta-diketones and beta-keto esters. The target compounds were synthesized in the highest yields from beta-keto esters (45-90%) and in somewhat lower yields from beta-diketones (46-75%) and malonates (37-67%).
Terent'ev
Alexander O
AO
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation. terentev@ioc.ac.ru
Borisov
Dmitry A
DA
Yaremenko
Ivan A
IA
Chernyshev
Vladimir V
VV
Nikishin
Gennady I
GI
D002384:Catalysis; D007659:Ketones / Q000737:chemistry*; D010545:Peroxides / Q000138:chemical synthesis* / Q000737:chemistry; D028561:Transition Elements / Q000737:chemistry*; D020122:tert-Butylhydroperoxide / Q000737:chemistry*
D007659:Ketones; D010545:Peroxides; D028561:Transition Elements; D020122:tert-Butylhydroperoxide