Total synthesis of the antibiotic kendomycin: a macrocyclization using the Tsuji-Trost etherification
Tetsuya Sengoku1, Shu Xu, Kenji Ogura
1Graduate 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).
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.
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