角状取代的1-氮杂双环环系的对映选择性合成：使用氮杂-Cope重排的动态动力学拆分
Enantioselective synthesis of angularly substituted 1-azabicyclic ring systems: dynamic kinetic resolution using aza-Cope rearrangements.
作者信息
Ito Tatsuya, Overman Larry E, Wang Jocelyn
机构信息
Department of Chemistry, University of California, Irvine, 1102 Natural Sciences II, Irvine, California 92697-2025, USA.
出版信息
J Am Chem Soc. 2010 Mar 17;132(10):3272-3. doi: 10.1021/ja100607z.
Abstract
A useful enantioselective synthesis of angularly substituted 1-azabicyclic molecules that delivers the bicyclic amine products in good yield and 99% ee is reported. Angularly substituted cis-octahydrocyclopenta[b]pyrroles, cis-octahydroindoles, cis-decahydrocyclohepta[b]pyrroles, and cis-octahydrocyclopenta[b]pyridine are formed in good yields and 99% ee exclusively as the cis stereoisomers. Decahydroquinolines are generated as mixtures of cis and trans stereoisomers in similarly high ee. The starting materials for this cascade transformation are assembled in five steps from cycloalkanones and enantiomerically pure (R)-2-phenyl-3-butenamine. This enantioselective synthesis introduces a new strategy for dynamic kinetic resolution in which a rapid tautomeric equilibration of diastereomeric iminium cations is combined with a diastereoselective sigmatropic rearrangement.
摘要
报道了一种有用的对映选择性合成角取代的1-氮杂双环分子的方法，该方法能以良好的产率和99%的对映体过量（ee）得到双环胺产物。角取代的顺式八氢环戊并[b]吡咯、顺式八氢吲哚、顺式十氢环庚并[b]吡咯和顺式八氢环戊并[b]吡啶以良好的产率和99%的ee形成，且仅作为顺式立体异构体。十氢喹啉以顺式和反式立体异构体的混合物形式生成，对映体过量同样很高。这种串联转化的起始原料由环烷酮和对映体纯的（R）-2-苯基-3-丁烯胺分五步组装而成。这种对映选择性合成引入了一种动态动力学拆分的新策略，其中非对映体亚胺离子的快速互变异构平衡与非对映选择性[3,3] - 迁移重排相结合。
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