Kang YoungKu, Chen Weijie, Breugst Martin, Seidel Daniel
Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey , Piscataway, New Jersey 08854, United States.
Department für Chemie, Universität zu Köln , Greinstraße 4, 50939 Köln, Germany.
J Org Chem. 2015 Oct 2;80(19):9628-40. doi: 10.1021/acs.joc.5b01384.
Cyclic amines such as 1,2,3,4-tetrahydroisoquinoline undergo regiodivergent annulation reactions with 4-nitrobutyraldehydes. These redox-neutral transformations enable the asymmetric synthesis of highly substituted polycyclic ring systems in just two steps from commercial materials. The utility of this process is illustrated in a rapid synthesis of (-)-protoemetinol. Computational studies provide mechanistic insights and implicate the elimination of acetic acid from an ammonium nitronate intermediate as the rate-determining step.
环状胺类，如1,2,3,4-四氢异喹啉，可与4-硝基丁醛发生区域发散性环化反应。这些氧化还原中性转化能够从商业原料出发，仅通过两步反应就实现高度取代的多环体系的不对称合成。（-）-原依米丁醇的快速合成展示了该方法的实用性。计算研究提供了机理见解，并表明从硝酸铵中间体消除乙酸是速率决定步骤。
