title: Novel and stereocontrolled synthesis of (+/-)-tetrodotoxin from myo-inositol.
abstract: [reactions: see text] The novel and stereocontrolled synthesis of (+/-)-tetrodotoxin from myo-inositol is described. The key steps involve the stepwise oxidation of hydroxyl groups to the carbonyl function, followed by the addition of specific nucleophiles, including the successive spiro alpha-chloroepoxide formation and its ring-opening with the azide anion, to give the desired branched chain structures (5-->6, 17-->18-->19-->20 and 23-->24-->25) with the desired regio- and stereoselectivities in high yields. The stepwise conversion of the alpha-azido aldehyde 25 to the delta-lactone 29, followed by reduction of the azide, introduction of a guanidine moiety, aldehyde formation, and deprotection, produced the (+/-)-tetrodotoxin.
authors.affiliation: Laboratory of Organic Chemistry, Faculty of Engineering, Kanagawa University, 3-27-1, Rokkakubashi, Kanagawa-ku, Yokohama, 221-8686 Japan. satouk01@kanagawa-u.ac.jp
authors.forename: Ken-ichi
authors.initials: K
authors.lastname: Sato
authors.forename: Shoji
authors.initials: S
authors.lastname: Akai
authors.forename: Naoki
authors.initials: N
authors.lastname: Sugita
authors.forename: Tadatsugu
authors.initials: T
authors.lastname: Ohsawa
authors.forename: Tomokazu
authors.initials: T
authors.lastname: Kogure
authors.forename: Hirotsugu
authors.initials: H
authors.lastname: Shoji
authors.forename: Juji
authors.initials: J
authors.lastname: Yoshimura
mesh_terms: D013237:Stereoisomerism; D013779:Tetrodotoxin / Q000138:chemical synthesis*
chemical_list: D013779:Tetrodotoxin