Forbeck Erin M, Evans Cory D, Gilleran John A, Li Pixu, Joullié Madeleine M
Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104, USA.
J Am Chem Soc. 2007 Nov 21;129(46):14463-9. doi: 10.1021/ja0758077. Epub 2007 Oct 31.
A thorough investigation of a regio- and stereospecific aziridine ring opening reaction presents new synthetic technology for the construction of a variety of quaternary beta-substituted-alpha-amino functional groups. Mild, metal-free reaction conditions allow for application in highly functionalized systems. This reaction has been applied to the challenging stereoselective formation of tertiary alkyl-aryl ethers. The strategy for the formation of these hindered ethers has been investigated using a variety of functionalized aziridines and phenols to determine the scope of the reaction. Other nucleophiles, such as thiolate, azide, and chloride, have also been examined to encompass the synthesis of a broader range of functionalities. This aziridine ring opening reaction manifold has demonstrated utility in assembling: beta-substituted-alpha-amino carboxamides, beta-substituted-alpha-amino esters, beta-substituted-alpha-amino silyl ethers, beta-thio-alpha-amino carboxamides, beta-azido-alpha-amino carboxamides, and beta-halo-alpha-amino carboxamides. Studies to probe the effect of the aziridine substitution patterns show that alkyl aziridines display similar reactivity to alkynyl aziridines, giving insight into mechanistic possibilities.
对区域和立体特异性氮丙啶开环反应进行全面研究，为构建多种季碳β-取代-α-氨基官能团提供了新的合成技术。温和的无金属反应条件使其可应用于高度官能化的体系。该反应已应用于具有挑战性的叔烷基-芳基醚的立体选择性形成。使用多种官能化氮丙啶和酚类研究了这些受阻醚的形成策略，以确定反应范围。还研究了其他亲核试剂，如硫醇盐、叠氮化物和氯化物，以涵盖更广泛功能的合成。这种氮丙啶开环反应体系已证明可用于组装：β-取代-α-氨基羧酰胺、β-取代-α-氨基酯、β-取代-α-氨基硅醚、β-硫代-α-氨基羧酰胺、β-叠氮基-α-氨基羧酰胺和β-卤代-α-氨基羧酰胺。探究氮丙啶取代模式影响的研究表明，烷基氮丙啶与炔基氮丙啶表现出相似的反应性，为反应机理提供了线索。
