title: Tremorgenic indole alkaloids. The total synthesis of (-)-penitrem D.
abstract: A convergent, stereocontrolled total synthesis of the architecturally complex tremorgenic indole alkaloid (-)-penitrem D (4) has been achieved. Highlights of the synthesis include an efficient, asymmetric synthesis of the western hemisphere; the stereocontrolled assembly of the I-ring; discovery of a novel autoxidation to introduce the C(22) tertiary hydroxyl group, required for tremorgenic activity; union of fully elaborated eastern and western hemispheres, exploiting an indole synthetic protocol developed expressly for this purpose; and a late-stage, stereoselective construction of the A and F rings exploiting a Sc(OTf)(3-)promoted reaction cascade. The longest linear sequence leading to (-)-penitrem D (4) was 43 steps.
authors.affiliation: Department of Chemistry, Monell Chemical Senses Center, University of Pennsylvania, Philadelphia, PA 19104, USA. smithab@sas.upenn.edu
authors.forename: Amos B
authors.initials: AB
authors.lastname: Smith
authors.forename: Naoki
authors.initials: N
authors.lastname: Kanoh
authors.forename: Haruaki
authors.initials: H
authors.lastname: Ishiyama
authors.forename: Noriaki
authors.initials: N
authors.lastname: Minakawa
authors.forename: Jon D
authors.initials: JD
authors.lastname: Rainier
authors.forename: Richard A
authors.initials: RA
authors.lastname: Hartz
authors.forename: Young Shin
authors.initials: YS
authors.lastname: Cho
authors.forename: Haifeng
authors.initials: H
authors.lastname: Cui
authors.forename: William H
authors.initials: WH
authors.lastname: Moser
mesh_terms: D026121:Indole Alkaloids / Q000737:chemistry*; D009183:Mycotoxins / Q000138:chemical synthesis*; D010407:Penicillium / Q000737:chemistry
chemical_list: D026121:Indole Alkaloids; D009183:Mycotoxins; C003626:tremortin