title: Formal total syntheses of the (-)-salicylihalamides A and B from D-glucose and L-rhamnose.
abstract: [reaction: see text] Two formal total syntheses of the (-)-salicylihalamides, based on chiral pool approaches, are reported. D-glucose and L-rhamnose were used to prepare advanced intermediates 23 and 54, which can be converted in three or four steps, respectively, to the target compounds. The synthesis of 23 from a known D-glucose-derivative was accomplished in 12 steps and 17% overall yield, and the synthesis of 54 from a known L-rhamnose-derivative was done in nine steps and 6% overall yield. A key step in the synthesis was a ring-closing metathesis reaction to prepare the macrocyclic ring system. It was demonstrated that the phenolic protecting group was critical for inducing the preferential formation of the desired E isomer. It was further shown that the protecting group at the C13 hydroxyl group had no significant influence on the E:Z ratio during the ring-closing metathesis reaction.
authors.affiliation: Department of Medicinal Chemistry, Center for Cancer Experimental Therapeutics and Center for Drug Discovery, Higuchi Biosciences Center, University of Kansas, 1251 Wescoe Hall Drive, Lawrence, Kansas 66045-7582, USA.
authors.forename: Torsten
authors.initials: T
authors.lastname: Haack
authors.forename: KyoungLang
authors.initials: K
authors.lastname: Haack
authors.forename: Wibke E
authors.initials: WE
authors.lastname: Diederich
authors.forename: Burchelle
authors.initials: B
authors.lastname: Blackman
authors.forename: Subho
authors.initials: S
authors.lastname: Roy
authors.forename: Srinivas
authors.initials: S
authors.lastname: Pusuluri
authors.forename: Gunda I
authors.initials: GI
authors.lastname: Georg
mesh_terms: D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis*; D005947:Glucose; D012210:Rhamnose; D013237:Stereoisomerism
chemical_list: D019086:Bridged Bicyclo Compounds, Heterocyclic; C410986:salicylihalamide A; D005947:Glucose; D012210:Rhamnose