title: Enantiodivergent synthesis of either enantiomer of ABCDE-ring analogue of antitumor antibiotic fredericamycin A via intramolecular [4 + 2] cycloaddition approach.
abstract: [reaction: see text] An intramolecular enantiodivergent synthesis of both enantiomers of the ABCDE-ring analogue 22 of fredericamycin A is reported. Key steps involve an intramolecular [4 + 2] cycloaddition of 17 and an aromatic Pummerer-type reaction of 19. A lipase-catalyzed enantioselective desymmetrization of prochiral diol 2 using 1-ethoxyvinyl 2-furoate 3 led to the pivotal intermediate (R)-4.
authors.affiliation: Graduate School of Pharmaceutical Sciences, Osaka University, 1-6, Yamadaoka, Suita, Osaka 565-0871, Japan.
authors.forename: S
authors.initials: S
authors.lastname: Akai
authors.forename: T
authors.initials: T
authors.lastname: Tsujino
authors.forename: N
authors.initials: N
authors.lastname: Fukuda
authors.forename: K
authors.initials: K
authors.lastname: Iio
authors.forename: Y
authors.initials: Y
authors.lastname: Takeda
authors.forename: K
authors.initials: K
authors.lastname: Kawaguchi Ki
authors.forename: T
authors.initials: T
authors.lastname: Naka
authors.forename: K
authors.initials: K
authors.lastname: Higuchi
authors.forename: Y
authors.initials: Y
authors.lastname: Kita
mesh_terms: D000903:Antibiotics, Antineoplastic / Q000138:chemical synthesis / Q000737:chemistry*; D002175:Candida / Q000201:enzymology; D002942:Circular Dichroism; D006801:Humans; D007546:Isoquinolines / Q000138:chemical synthesis / Q000737:chemistry*; D008049:Lipase / Q000378:metabolism; D008968:Molecular Conformation; D015394:Molecular Structure; D019906:Nuclear Magnetic Resonance, Biomolecular; D013141:Spiro Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000903:Antibiotics, Antineoplastic; D007546:Isoquinolines; D013141:Spiro Compounds; D008049:Lipase; C016660:fredericamycin A