Total synthesis of the antibiotic kendomycin: a macrocyclization using the Tsuji-Trost etherification

  • Angew Chem Int Ed Engl. 2014 Apr 14;53(16):4213-6. doi: 10.1002/anie.201400305.
Tetsuya Sengoku  1 ,  Shu Xu ,  Kenji Ogura ,  Yoshinori Emori ,  Kenji Kitada ,  Daisuke Uemura ,  Hirokazu Arimoto
Affiliations
  • 1. 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).
PMID: 24623596 DOI: 10.1002/anie.201400305
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.

Keywords
antibiotics; macrocycles; natural products; palladium; total synthesis.
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