Synthesis 2019; 51(06): 1419-1426
DOI: 10.1055/s-0037-1611707
paper
© Georg Thieme Verlag Stuttgart · New York

Facile Total Synthesis of Thailandepsins D–F: Novel Bicyclic Depsipeptide Histone Deacetylase Inhibitors Isolated from a Microorganism

Noel Sayar
,
Koichi Narita
,
Faculty of Pharmaceutical Sciences, Tohoku Medical and Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan   Email: katoh@tohoku-mpu.ac.jp
› Author Affiliations
This study was financially supported by a JSPS KAKENHI (Grant Number: JP15k07865) and a Grant-in-Aid for Strategic Research Foundation Program at Private Universities (Grant Number: S15110010L) from Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT).
Further Information

Publication History

Received: 12 November 2018

Accepted after revision: 24 November 2018

Publication Date:
01 February 2019 (online)


Dedicated to Professor Kiyoshi Tomioka, Doshisha Women’s College, Japan on his 70th birthday

Abstract

The naturally occurring bicyclic depsipeptide histone deacetylase inhibitors thailandepsins D–F were efficiently synthesized for the first time in 49–61% overall yield over five steps, starting from known amine and carboxylic acid segments. The synthesis includes the condensation of the two known starting materials to directly assemble the corresponding seco-acids, which are the key precursors for macrolactonization. The seco-acids are then macrolactonized using the Shiina method to construct the requisite 15-member macrocycles.

Supporting Information

 
  • References

  • 1 Wang C, Henkes LM, Doughty LB, He M, Wang D, Meyer-Almes FJ, Cheng Y.-Q. J. Nat. Prod. 2011; 74: 2031
  • 2 Wang C, Flemming CJ, Cheng Y.-Q. Med. Chem. Commun. 2012; 3: 976
  • 3 Biggins JB, Gleber CD, Brady SF. Org. Lett. 2011; 13: 1536
  • 4 HDAC inhibitory data for thailandepsins A–F (16) along with reference compound FK228 have been reported,2 and are as follows: FK228: IC50 = 0.31 nM; 1: IC50 = 0.28 nM; 2: IC50 = 1.2 nM; 3: IC50 = 0.20 nM; 4: IC50 = 0.48 nM; 5: IC50 = 0.94 nM; and 6: IC50 = 2.6 nM.
  • 5 Benelkebir H, Donlevy AM, Packham G, Ganesan A. Org. Lett. 2011; 13: 6334
  • 6 Liu JY, Ma X, Liu Y, Wang Z, Kwong S, Ren Q, Tang S, Meng Y, Xu Z, Ye T. Synlett 2012; 23: 783
  • 7 Fukui Y, Narita K, Dan S, Yamori T, Ito A, Yoshida M, Katoh T. Eur. J. Med. Chem. 2014; 76: 301
  • 8 Cheng Y.-Q, Yang S, Wang P. (ChinAn PharmaTech Wuhan Co., Ltd., China) PCT WO 131355A1, 2015
  • 9 Narita K, Katoh T. Chem. Pharm. Bull. 2016; 64: 913
  • 10 Narita K, Sayar N, Saijo K, Ishioka C, Katoh T. Synthesis 2019; DOI: 10.1055/s-0037-1612059.
    • 11a Narita K, Kikuchi T, Watanabe K, Takizawa T, Yamori T, Yoshida M, Katoh T. Chem. Eur. J. 2009; 15: 11174
    • 11b Takizawa T, Watanabe K, Narita K, Kudo K, Oguchi T, Abe H, Katoh T. Heterocycles 2008; 76: 275
  • 12 Narita K, Fukui Y, Sano Y, Yamori T, Ito A, Yoshida M, Katoh T. Eur. J. Med. Chem. 2013; 60: 295
  • 13 Shiina I, Katoh T, Nagai S, Hashizume M. Chem. Rec. 2009; 9: 305