title: Rhodium-catalyzed cyclohydrocarbonylation approach to the syntheses of enantiopure homokainoids.
abstract: Homologues of kainic acid, a naturally occurring potent glutamate receptor agonist, were designed based on a rigidified pipecolinoglutamic acid structure and can be regarded as homokainoids for their potential activities in the central nervous system. These novel homokainoids in an enantiomerically pure form were synthesized from enantiopure (R)- and (S)-Garner's aldehyde, featuring (i) the highly diastereoselective addition of alkenylcuprates to the acrylate intermediates and (ii) the Rh-catalyzed cyclohydrocarbonylation of homoallylic amine intermediates to construct the functionalized piperidine moiety in the key steps. For the introduction of a substituent at the 4- or 5-position of pipecolinoglutamic acid, a few different strategies were used, which successfully led to the formation of enantiopure homokainoids.
authors.affiliation: Department of Chemistry, State University of New York at Stony Brook, Stony Brook, NY 11794-3400, USA.
authors.forename: Wen-Hua
authors.initials: WH
authors.lastname: Chiou
authors.forename: Angèle
authors.initials: A
authors.lastname: Schoenfelder
authors.forename: Liang
authors.initials: L
authors.lastname: Sun
authors.forename: André
authors.initials: A
authors.lastname: Mann
authors.forename: Iwao
authors.initials: I
authors.lastname: Ojima
mesh_terms: D002384:Catalysis; D018360:Crystallography, X-Ray; D003500:Cyclization; D006844:Hydrocarbons, Cyclic / Q000737:chemistry*; D007608:Kainic Acid / Q000031:analogs & derivatives* / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D006844:Hydrocarbons, Cyclic; D012238:Rhodium; D007608:Kainic Acid