J Org Chem. 2014 Feb 7;79(3):1356-67. doi: 10.1021/jo402759v.
The diastereoselective addition of an allylic indium intermediate to chiral o-bromophenyl sulfinyl imine 4 proceeded with good levels of diastereoselectivity. The resulting homoallylic amine derivatives were transformed into lactams 7 and 12, which upon copper-mediated intramolecular N-arylation led to the formation of benzo-fused 1-azabicyclo[j.k.0]alkanes 8 and 13. Benzo-fused 2-allyl-substituted heterocycles 14 could also be prepared by means of a palladium-catalyzed N-arylation of the corresponding free amines. The synthesis of the alkaloid (−)-angustureine was easily accomplished from (S)-2-allyltetrahydroquinoline (14b).
手性邻溴苯基亚砜亚胺 4 与烯丙基铟中间体的非对映选择性加成反应具有很好的非对映选择性。所得的同烯丙基胺衍生物被转化为内酰胺 7 和 12，它们在铜介导的分子内 N-芳基化作用下形成苯并稠合的 1-氮杂双环[j.k.0]烷 8 和 13。通过相应游离胺的钯催化 N-芳基化反应，也可以制备苯并稠合的 2-烯丙基取代杂环 14。从（S）-2-烯丙基四氢喹啉（14b）很容易完成生物碱（-）-angustureine 的合成。
