title: Total synthesis of the antibiotic kendomycin: a macrocyclization using the Tsuji-Trost etherification.
abstract: A highly stereocontrolled, convergent total synthesis of kendomycin [(-)-TAN2162], an ansa-macrocyclic antibiotic, is reported. The key of the strategy is an unprecedented Tsuji-Trost macrocyclic etherification, followed by a transannular Claisen rearrangement to construct the 18-membered carbocyclic framework. The oxa-six- and five-membered rings were also stereoselectively constructed respectively by a cascade oxidative cyclization at an unfunctionalized benzylic position and using a one-pot epoxidation/5-exo-tet epoxide opening.
authors.affiliation: Graduate School of Life Sciences, Tohoku University, 2-1-1 Katahira, Sendai 980-8577 (Japan) http://www.agri.tohoku.ac.jp/bunseki/index-j.html; Current address: Department of Materials Science, Faculty of Engineering, Shizuoka University, Shizuoka 432-8561 (Japan).
authors.forename: Tetsuya
authors.initials: T
authors.lastname: Sengoku
authors.forename: Shu
authors.initials: S
authors.lastname: Xu
authors.forename: Kenji
authors.initials: K
authors.lastname: Ogura
authors.forename: Yoshinori
authors.initials: Y
authors.lastname: Emori
authors.forename: Kenji
authors.initials: K
authors.lastname: Kitada
authors.forename: Daisuke
authors.initials: D
authors.lastname: Uemura
authors.forename: Hirokazu
authors.initials: H
authors.lastname: Arimoto
mesh_terms: D000900:Anti-Bacterial Agents / Q000138:chemical synthesis*; D004987:Ethers / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D017828:Rifabutin / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000900:Anti-Bacterial Agents; D004987:Ethers; C485395:kendomycin; D017828:Rifabutin
keywords: antibiotics; macrocycles; natural products; palladium; total synthesis