Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (China).
Angew Chem Int Ed Engl. 2015 Jan 19;54(4):1231-5. doi: 10.1002/anie.201408874. Epub 2014 Nov 25.
The interception of cobalt-based carbene radicals with α-aminoalkyl radicals was combined with the Kornblum-DeLaMare reaction and provides β-ester-γ-amino ketones, which are otherwise difficult to obtain in high chemoselectivity. Mechanistically, this transformation is an interplay of cobalt-based carbene radicals, organoradicals, and ionic intermediates and involves the construction of two C-C bonds and one C=O bond in a one-pot process. The reaction also features a wide substrate scope and is highly efficient and insensitive to moisture and air.
钴卡宾自由基与α-氨烷基自由基的拦截与 Kornblum-DeLaMare 反应相结合,提供了β-酯-γ-氨基酮,否则很难获得高化学选择性。从机理上讲,这种转化是钴基卡宾自由基、有机自由基和离子中间体的相互作用,涉及在一锅过程中构建两个 C-C 键和一个 C=O 键。该反应还具有广泛的底物范围,具有高效、对水分和空气不敏感的特点。