Total Synthesis of Clostrienose

Shunya Takahashi; Takenori Hama; Toshihiko Nogawa; Narihito Ogawa; Hiroyuki Koshino

doi:10.1021/acsomega.3c05277

Total Synthesis of Clostrienose

ACS Omega. 2023 Sep 11;8(38):35382-35392. doi: 10.1021/acsomega.3c05277. eCollection 2023 Sep 26.

Authors

Shunya Takahashi¹, Takenori Hama^{1

2}, Toshihiko Nogawa¹, Narihito Ogawa², Hiroyuki Koshino¹

Affiliations

¹ RIKEN Center for Sustainable Resource Science, Wako, Saitama 351-0198, Japan.
² Department of Applied Chemistry, Meiji University, 1-1-1, Higashimita, Tama-ku, Kawasaki 214-8571, Japan.

Abstract

This paper considers the total synthesis of a cellular differentiation regulator of Clostridium acetobutylicum, clostrienose, which is a unique fatty-acid glycosyl ester consisting of clostrienoic acid, (3R,5E,8E,10E)-3-hydroxy-tetradeca-5,8,10-trienoic acid and α-d-galactofuranosyl-(1 → 2)-α-l-rhamnose. The key features of our synthesis include stereoselective construction of a skipped-triene system in clostrienoic acid and its esterification with a disaccharide residue. The partially protected clostrienoic acid employed for the coupling also served for the preparation of l-rhamnosyl clostrienoate, thus leading to confirmation of the proposed structure unambiguously.