title: Phosphate tether-mediated approach to the formal total synthesis of (-)-salicylihalamides A and B.
abstract: A concise formal synthesis of the cytotoxic macrolides (-)-salicylihalamides A and B is reported. Key features of the synthetic strategy include a chemoselective hydroboration, highly regio- and diastereoselective methyl cuprate addition, Pd-catalyzed formate reduction, and an E-selective ring-closing metathesis to construct the 12-membered macrocycle subunit. Overall, two routes have been developed from a readily prepared bicyclic phosphate (4 steps), a 13-step route and a more efficient 9-step sequence relying on regioselective esterification of a key diol.
authors.affiliation: Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Lawrence, Kansas 66045, United States.
authors.forename: Rambabu
authors.initials: R
authors.lastname: Chegondi
authors.forename: Mary M L
authors.initials: MM
authors.lastname: Tan
authors.forename: Paul R
authors.initials: PR
authors.lastname: Hanson
mesh_terms: D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000737:chemistry*; D002384:Catalysis; D004951:Esterification; D010165:Palladium / Q000737:chemistry; D010710:Phosphates / Q000737:chemistry*; D013379:Substrate Specificity
chemical_list: D019086:Bridged Bicyclo Compounds, Heterocyclic; D010710:Phosphates; C410986:salicylihalamide A; D010165:Palladium