Yao Lei, Aubé Jeffrey
Department of Medicinal Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Malott Hall, Room 4070, Lawrence, Kansas 66045-7852, USA.
J Am Chem Soc. 2007 Mar 14;129(10):2766-7. doi: 10.1021/ja068919r. Epub 2007 Feb 16.
The regiochemistry of the intramolecular Schmidt reaction of 2-substituted ketones has proved susceptible to control by the placement of an aromatic group at an adjacent position, permitting the selective formation of a series of bridged bicyclic lactams from these substrates. This phenomenon is ascribed to the presence of stabilizing through-space interactions between the positively charged leaving group and the aromatic substituents in a key azidohydrin intermediate.
2-取代酮分子内施密特反应的区域化学已证明可通过在相邻位置引入芳基来控制,从而能够从这些底物选择性地形成一系列桥连双环内酰胺。这种现象归因于关键叠氮醇中间体中带正电荷的离去基团与芳基取代基之间存在稳定的空间相互作用。