title: Syntheses of biologically active natural products and leading compounds for new pharmaceuticals employing effective construction of a polycyclic skeleton.
abstract: Cascade reactions are useful methods for the construction of polycyclic skeletons, which are important cores for biological activities. A variety of cascade reactions carried out under multiple reaction conditions, such as pericyclic, polar, radical, and transition metal-catalyzed reaction conditions, have been investigated. Culmorin, pentalenene, pentalenic acid, deoxypentalenic acid, longiborneol, cedrandiol, 8,14-cedranoxide, atisirene, atisine, and estrane-type steroids were synthesized via the intramolecular double Michael reaction. Aza double Michael reaction was applied to the syntheses of tylophorine, epilupinine, tacamonine, and paroxetine. Furthermore, sequential Michael and aldol reactions were performed in both intramolecular and intermolecular manners, leading to the formation of polycyclic compounds fused to a four-membered ring. Synthesis of paesslerin A utilizing a multicomponent cascade reaction revealed an error in the proposed structure. Unique cascade reactions carried out under radical and transition metal-catalyzed reaction conditions were also investigated. With the combination of several cascade reactions, serofendic acids and methyl 7beta-hydroxykaurenoate, both of which have neuroprotective activity, were synthesized in a selective manner.
authors.affiliation: Graduate School of Pharmaceutical Sciences, Tohoku University, Aobayama, Sendai 980-8578, Japan. mihara@mail.pharm.tohoku.ac.jp
authors.forename: Masataka
authors.initials: M
authors.lastname: Ihara
mesh_terms: D000470:Alkaloids / Q000138:chemical synthesis / Q000737:chemistry; D001688:Biological Products / Q000096:biosynthesis*; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis / Q000737:chemistry; D002626:Chemistry, Pharmaceutical; D007212:Indolizines / Q000138:chemical synthesis / Q000737:chemistry; D008956:Models, Chemical; D010087:Oxides / Q000737:chemistry; D010616:Phenanthrenes / Q000138:chemical synthesis / Q000737:chemistry; D011083:Polycyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D012717:Sesquiterpenes / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000470:Alkaloids; D001688:Biological Products; D001643:Bridged Bicyclo Compounds; D007212:Indolizines; D010087:Oxides; D010616:Phenanthrenes; D011083:Polycyclic Compounds; D012717:Sesquiterpenes; C013900:culmorin; C412581:longiborneol; C004218:tylophorine