title: Stereocontrolled Synthesis of a Possible Stereoisomer of Laurenidificin and a Formal Total Synthesis of (+)-Aplysiallene Featuring a Stereospecific Ring Contraction.
abstract: We report a highly stereocontrolled total synthesis of one of the possible stereoisomers of laurenidificin. Highlights of the synthesis include the formation of the 2,6-dioxabicyclo[3.3.0]octane framework by a stereospecific bromolactonization-α-bromination-ring contraction sequence, followed by a stereoselective propargylation, an insertion of the Z-enyne side chain by a hydroindation/cross coupling reaction, and ethylation at C13 with an organocuprate reagent. While the synthetic compound was not identical to the natural product, the absolute stereochemistry of the natural product was proposed on the basis of NMR analyses. Moreover, a formal total synthesis of (+)-aplysiallene was achieved by extending the ring contraction strategy.
authors.affiliation: Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology , 5-16-1 Ohmiya, Asahi-ku, Osaka 535-8585, Japan.
authors.forename: Shoji
authors.initials: S
authors.lastname: Kobayashi
authors.affiliation: Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology , 5-16-1 Ohmiya, Asahi-ku, Osaka 535-8585, Japan.
authors.forename: Taiki
authors.initials: T
authors.lastname: Yokoi
authors.affiliation: Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology , 5-16-1 Ohmiya, Asahi-ku, Osaka 535-8585, Japan.
authors.forename: Tomoharu
authors.initials: T
authors.lastname: Inoue
authors.affiliation: Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology , 5-16-1 Ohmiya, Asahi-ku, Osaka 535-8585, Japan.
authors.forename: Yutaka
authors.initials: Y
authors.lastname: Hori
authors.affiliation: Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology , 5-16-1 Ohmiya, Asahi-ku, Osaka 535-8585, Japan.
authors.forename: Tomoaki
authors.initials: T
authors.lastname: Saka
authors.affiliation: Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology , 5-16-1 Ohmiya, Asahi-ku, Osaka 535-8585, Japan.
authors.forename: Taiki
authors.initials: T
authors.lastname: Shimomura
authors.affiliation: Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology , 5-16-1 Ohmiya, Asahi-ku, Osaka 535-8585, Japan.
authors.forename: Araki
authors.initials: A
authors.lastname: Masuyama
mesh_terms: D001688:Biological Products; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D005663:Furans / Q000138:chemical synthesis* / Q000737:chemistry; D054879:Halogenation; D007202:Indicators and Reagents / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: C000609863:2,6-dioxabicyclo(3.3.0)octane; D001688:Biological Products; D019086:Bridged Bicyclo Compounds, Heterocyclic; D005663:Furans; D007202:Indicators and Reagents; C432927:aplysiallene; C000609862:laurenidificin