N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation.
J Org Chem. 2010 Aug 6;75(15):5065-71. doi: 10.1021/jo100793j.
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%).
人们发现过渡金属（铜、铁、锰、钴）可以催化β-二羰基化合物在叔丁基过氧化氢作用下的α-位置过氧反应。现已开发出一种选择性好、实验操作方便、克级规模的方法，用于合成β-二酮、β-酮酯和丙二酸二乙酯的α-过氧衍生物。在与β-二酮和β-酮酯的反应中，叔丁基过氧化氢和二羰基化合物的摩尔比实际上是（2-3/1）。β-酮酯的目标化合物的合成收率最高（45-90%），β-二酮的收率略低（46-75%），丙二酸二乙酯的收率较低（37-67%）。
