亚硝鎓离子介导的烯烃双环化反应：(-)-苦马豆素的全合成。
Nitrenium ion-mediated alkene bis-cyclofunctionalization: total synthesis of (-)-swainsonine.
机构信息
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607-7061, United States.
出版信息
Org Lett. 2011 May 6;13(9):2376-9. doi: 10.1021/ol2006117. Epub 2011 Apr 12.
Abstract
The total synthesis of (-)-swainsonine from 2,3-O-isopropylidene-D-erythrose in 12 steps and an overall yield of 28% is reported. The pivotal transformation in our route to this indolizidine alkaloid is the formation of the pyrrolidine ring and C-8a/8 stereodiad through the diastereoselective, bis-cyclofunctionalization of an γ,δ-unsaturated O-alkyl hydroxamate. This transformation is believed to proceed via the intramolecular capture of an N-acyl-N-alkoxyaziridinium ion generated by the diastereoselective addition of a singlet acylnitrenium ion to the pendant alkene.
摘要
从 2,3-O-亚异丙基-D-赤藓糖出发，经 12 步反应以 28%的总收率完成了 (-)-苦马豆素的全合成。在这条吲哚里西啶生物碱路线中，关键的转化是通过γ,δ-不饱和 O-烷基羟胺的立体选择性双环化反应形成吡咯烷环和 C-8a/8 立体二联体。据信，这种转化是通过通过立体选择性地将单重酰基氮宾离子加成到侧链烯上生成的 N-酰基-N-烷氧基氮鎓离子的分子内捕获来进行的。
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