title: The first total synthesis of discorhabdin A.
abstract: The first stereoselective total synthesis of a potent antitumor alkaloid, discorhabdin A (1), which is a unique sulfur-containing pyrroloiminoquinone alkaloid, is described. The key step in the stereocontrolled total synthesis of 1 involves both a diastereoselective oxidative spirocyclization using a hypervalent iodine(III) reagent and an efficient construction of the labile and highly strained N,S-acetal skeleton. These methodologies provide a breakthrough in the total syntheses of these promising new antitumor agents, discorhabdins and their analogues, which should serve as valuable probes for structure-activity studies.
authors.affiliation: Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamada-oka, Suita, Osaka 565-0871, Japan.
authors.forename: Hirofumi
authors.initials: H
authors.lastname: Tohma
authors.forename: Yu
authors.initials: Y
authors.lastname: Harayama
authors.forename: Miki
authors.initials: M
authors.lastname: Hashizume
authors.forename: Minako
authors.initials: M
authors.lastname: Iwata
authors.forename: Yorito
authors.initials: Y
authors.lastname: Kiyono
authors.forename: Masahiro
authors.initials: M
authors.lastname: Egi
authors.forename: Yasuyuki
authors.initials: Y
authors.lastname: Kita
mesh_terms: D000080:Acetals / Q000737:chemistry; D000970:Antineoplastic Agents / Q000138:chemical synthesis* / Q000737:chemistry; D003500:Cyclization; D009285:Naphthoquinones / Q000138:chemical synthesis / Q000737:chemistry; D010084:Oxidation-Reduction; D011809:Quinones / Q000138:chemical synthesis* / Q000737:chemistry*; D013141:Spiro Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism; D013455:Sulfur / Q000737:chemistry; D013841:Thiazepines / Q000138:chemical synthesis* / Q000737:chemistry*
chemical_list: D000080:Acetals; D000970:Antineoplastic Agents; D009285:Naphthoquinones; D011809:Quinones; D013141:Spiro Compounds; D013841:Thiazepines; C471812:discorhabdin A; D013455:Sulfur