title: Synthesis of biologically active (-)-dehydroiso-β-lapachone and the determination of its absolute configuration.
abstract: Synthesis of dehydoriso-β-lapachone (1) in both racemic and enantioenriched forms is achieved starting from reduced naphthoquinone equivalents. As for the synthesis of enantioenriched dehydroiso-β-lapachone, introduction of the asymmetric center was carried out by catalytic asymmetric epoxidation of the unfunctionalized trisubstituted olefin using Shi epoxidation diketal catalyst. The construction of isopropenylfurano-1,2-(β)-naphthoquinone was carried out by acidic ring-opening reaction of the epoxynaphthalene and the following diammonium cerium(IV) nitrate (CAN) oxidation. The absolute configuration of naturally occurring (-)-dehydroiso-β-lapachone was finally determined as (R) by comparing the measured optical rotation value of the synthetic (R)-dehydroiso-β-lapachone.
authors.affiliation: School of Pharmaceutical Sciences, Mukogawa Women's University, 11–68 Koshien Kyubancho, Nishinomiya, Hyogo, Japan. tkimachi@mukogawa-u.ac.jp
authors.forename: Tetsutaro
authors.initials: T
authors.lastname: Kimachi
authors.forename: Eri
authors.initials: E
authors.lastname: Torii
authors.forename: Yusuke
authors.initials: Y
authors.lastname: Kobayashi
authors.forename: Misae
authors.initials: M
authors.lastname: Doe
authors.forename: Motoharu
authors.initials: M
authors.lastname: Ju-ichi
mesh_terms: D002563:Cerium / Q000737:chemistry; D009285:Naphthoquinones / Q000138:chemical synthesis / Q000737:chemistry*; D009904:Optical Rotation; D010084:Oxidation-Reduction; D013237:Stereoisomerism
chemical_list: D009285:Naphthoquinones; C032786:cerium nitrate; D002563:Cerium; C014638:beta-lapachone