Biallas Phillip, Häring Andreas P, Kirsch Stefan F
Organic Chemistry, Bergische Universität Wuppertal, Gaußstraße 20, 42119 Wuppertal, Germany.
Org Biomol Chem. 2017 Apr 11;15(15):3184-3187. doi: 10.1039/c7ob00731k.
A mild and convenient protocol for the oxidative cleavage of 1,3-diketone compounds is described. Under metal-free conditions, the method converts the 1,3-dicarbonyls into amides when treated with (nBuN)N and iodine in the presence of an amine at room temperature. Using this method, a range of 1,3-dicarbonyls with various structural motifs including sterically demanding substituents and ordinary functional groups were easily fragmented, and it is demonstrated that cyclic 1,3-dicarbonyls can be directly transformed into acyclic diamides through ring-opening. Initial mechanistic studies show that diazidation of the enol form is followed by nucleophilic substitution with the amine.
描述了一种温和且简便的1,3 - 二酮化合物氧化裂解方法。在无金属条件下，该方法在室温下，于胺存在的情况下，用(nBuN)N和碘处理时，可将1,3 - 二羰基化合物转化为酰胺。使用此方法，一系列具有各种结构特征（包括空间位阻较大的取代基和普通官能团）的1,3 - 二羰基化合物易于裂解，并且证明环状1,3 - 二羰基化合物可通过开环直接转化为非环状二酰胺。初步机理研究表明，烯醇形式先进行重氮化，然后与胺发生亲核取代反应。
