The rearrangement of 2,3-epoxysulfonates and its application to natural products syntheses: formal synthesis of (-)-aphanorphine and total syntheses of (-)-alpha-herbertenol and (-)-herbertenediol |
| |
Authors: | Kita Yasuyuki Futamura Junko Ohba Yusuke Sawama Yoshinari Ganesh Jnaneshwara K Fujioka Hiromichi |
| |
Institution: | Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamada-oka, Suita, Osaka 565-0871, Japan. kita@phs.osaka-u.ac.jp |
| |
Abstract: | The Lewis acid treatment of 2,3-epoxysulfonates with 2,3-dialkyl substituents or 2-alkyl-3-aryl substituents produced the rearrangement products via C3-cleavage of the oxirane ring in high yields. On the other hand, 2-aryl-3-alkyl-2,3-epoxysulfonates produced the products via C2-cleavage of the oxirane ring. The sulfonyloxy groups of the alpha-sulfonyloxy ketones, having a chiral benzylic quaternary carbon center obtained by the rearrangement of 2-alkyl-3-aryl-2,3-epoxysulfonates, were reductively eliminated to give the ketones with a chiral benzylic quaternary carbon center. The method was applied to the formal synthesis of (-)-aphanorphine and total syntheses of (-)-alpha-herbertenol and (-)-herbertenediol. |
| |
Keywords: | |
本文献已被 PubMed 等数据库收录! |
|