桥联邻苯甲酰胺的分子内施密特反应合成、结构分析及反应性研究。
Synthesis, structural analysis, and reactivity of bridged orthoamides by intramolecular Schmidt reaction.
机构信息
Department of Medicinal Chemistry, University of Kansas, Structural Biology Center, 2121 Simons Drive, West Campus, Lawrence, Kansas 66047, USA.
出版信息
J Am Chem Soc. 2010 Mar 3;132(8):2530-1. doi: 10.1021/ja910654t.
Abstract
Intramolecular Schmidt reactions can be reliably steered toward bridged heterocycles containing orthoamides in high yields. The ketal tether enhances the control of regioselectivity in the migration of the bond distal to the reactive azide nucleophile, thus providing the first examples of the intramolecular Schmidt reaction proceeding with a complete regioselectivity en route to bridged products. The method is broad in scope and allows for systematic study of compounds that are analogous to elusive tetrahedral intermediates of amide addition reactions. Some initial reactivity and structural profiling of these compounds are also reported.
摘要
分子内施密特反应可以可靠地导向高产率的含邻酰胺桥环杂环化合物。缩酮键增强了对反应性叠氮亲核试剂远端键迁移的区域选择性控制，从而提供了首例完全区域选择性的分子内施密特反应生成桥接产物的例子。该方法具有广泛的应用范围，并允许对类似酰胺加成反应难以捉摸的四面体中间体的化合物进行系统研究。还报道了这些化合物的一些初始反应性和结构特征。
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