title: Synthesis of alkaloids by Stevens rearrangement of nitrile-stabilized ammonium ylides: (±)-laudanosine, (±)-laudanidine, (±)-armepavine, (±)-7-methoxycryptopleurine, and (±)-xylopinine.
abstract: The Stevens rearrangement of nitrile-stabilized ammonium ylides in conjunction with the reductive removal of the nitrile function permits the facile construction of α-branched amines from α-aminonitriles. We employed this reaction sequence for the preparation of (±)-laudanosine, (±)-laudanidine and (±)-armepavine, (±)-7-methoxycryptopleurine, and (±)-xylopinine from two closely related and readily accessible bicyclic α-aminonitriles. The final products were obtained in high to almost quantitative yields (71-98%) from the quaternary ammonium salts obtained by N-alkylation of these starting materials.
authors: Institute of Organic Chemistry, University of Mainz, Duesbergweg 10-14, D-55128 Mainz, Germany.
authors: Julio Cesar
authors: JC
authors: Orejarena Pacheco
authors: Günther
authors: G
authors: Lahm
authors: Till
authors: T
authors: Opatz
mesh_terms: D044182:Benzylisoquinolines / Q000138:chemical synthesis* / Q000737:chemistry; D001600:Berberine Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D007546:Isoquinolines / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*; D000644:Quaternary Ammonium Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D011807:Quinolizines / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: C518787:7-methoxycryptopleurine; D044182:Benzylisoquinolines; D001600:Berberine Alkaloids; D007546:Isoquinolines; D009570:Nitriles; D000644:Quaternary Ammonium Compounds; D011807:Quinolizines; C453820:xylopinine; C001522:laudanosine; C064689:armepavine