Tojino Mami, Uenoyama Yoshitaka, Fukuyama Takahide, Ryu Ilhyong
Department of Chemistry, Faculty of Arts and Sciences, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan.
Chem Commun (Camb). 2004 Nov 7(21):2482-3. doi: 10.1039/b408746a. Epub 2004 Sep 14.
Free-radical carbonylation of omega-alkynylamines with tributyltin hydride gives a mixture of alpha-methylene lactams and alpha-stannylmethylene lactams. Nucleophilic addition of an internal amino group to the carbonyl group of alpha-ketenyl radicals is proposed as the cyclization step. The subsequent unusual 1,4-H shift from the resulting 1-hydroxyallyl radical, followed by elimination of the beta-tributyltin radical leads to the formation of alpha-methylene lactams.
ω-炔基胺与三丁基氢化锡的自由基羰基化反应生成α-亚甲基内酰胺和α-锡亚甲基内酰胺的混合物。有人提出，环化步骤是内部氨基向α-烯酮基自由基的羰基进行亲核加成。随后，从生成的1-羟基烯丙基自由基发生不寻常的1,4-H迁移，接着消除β-三丁基锡自由基，从而导致α-亚甲基内酰胺的形成。
