Asymmetric Redox-Annulation of Cyclic Amines.
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.
Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey , Piscataway, New Jersey 08854, United States.
YoungKu
Y
Kang
Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey , Piscataway, New Jersey 08854, United States.
Weijie
W
Chen
Department für Chemie, Universität zu Köln , Greinstraße 4, 50939 Köln, Germany.
Martin
M
Breugst
Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey , Piscataway, New Jersey 08854, United States.
Daniel
D
Seidel
D000085:Acetates / Q000737:chemistry*; D000447:Aldehydes / Q000737:chemistry; D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D064751:Ammonium Compounds / Q000737:chemistry*; D002384:Catalysis; D015394:Molecular Structure; D010084:Oxidation-Reduction; D011789:Quantum Theory; D044005:Tetrahydroisoquinolines / Q000737:chemistry*
D000085:Acetates; D000447:Aldehydes; D000588:Amines; D064751:Ammonium Compounds; D044005:Tetrahydroisoquinolines; C018475:butyraldehyde