title: Biomimetic synthesis of equisetin and (+)-fusarisetin A.
abstract: (+)-Fusarisetin A belongs to a group of acyl tetramic acid natural products that show potential anticancer activity. Equisetin, a biogenetically related acyl tetramic acid, contains the basic skeleton of (+)-fusarisetin A. We proposed that equisetin and (+)-fusarisetin A share a biosynthetic pathway that starts with naturally occurring (S)-serine and an unsaturated fatty acid. In support of this hypothesis, we have demonstrated that a cyclization sequence involving an intramolecular Diels-Alder reaction followed by a Dieckmann cyclization of polyenoylamino acid yielded equisetin. The aerobic oxidation of equisetin, promoted by either Mn(III)/O2 or a reactive oxygen species (ROS) produced by visible-light chemistry, gave peroxyfusarisetin, which could be easily reduced to (+)-fusarisetin A. We report herein detailed information on the biogenetic synthesis of equisetin and (+)-fusarisetin A.
authors.affiliation: Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, 3663N Zhongshan Road, Shanghai 200062 (P. R. China), Fax: (+86) 21-62604784.
authors.forename: Jun
authors.initials: J
authors.lastname: Yin
authors.forename: Lili
authors.initials: L
authors.lastname: Kong
authors.forename: Cheng
authors.initials: C
authors.lastname: Wang
authors.forename: Yingbo
authors.initials: Y
authors.lastname: Shi
authors.forename: Shujun
authors.initials: S
authors.lastname: Cai
authors.forename: Shuanhu
authors.initials: S
authors.lastname: Gao
mesh_terms: D000972:Antineoplastic Agents, Phytogenic; D032701:Biomimetics; D003500:Cyclization; D061565:Cycloaddition Reaction; D006576:Heterocyclic Compounds, 4 or More Rings / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D011760:Pyrrolidinones / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013764:Tetrahydronaphthalenes / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D000972:Antineoplastic Agents, Phytogenic; D006576:Heterocyclic Compounds, 4 or More Rings; D011760:Pyrrolidinones; D013764:Tetrahydronaphthalenes; C572422:fusarisetin A; C009435:tetramic acid; C024509:equisetin
keywords: biomimetic synthesis; equisetin; fusarisetin A; radical reactions; total synthesis