Synthesis 2022; 54(03): 683-688
DOI: 10.1055/a-1652-3714
paper

Total Synthesis of Thiocladospolide A and Its C2-Epimer

Pramod Swami
,
Maruti Mali
,
Baswaraj Dhulshette
,
Subhash Ghosh
P.S. is grateful to the Council of Scientific and Industrial Research (CSIR), New Delhi, India for a fellowship.


Abstract

The first total synthesis of the recently isolated natural product thiocladospolide A, along with its C2-epimer, is achieved in nine straightforward linear steps and 12% overall yield. The key feature of the synthesis is the construction of the macrocyclic ring via a late-stage ring-closing metathesis reaction followed by alkene reduction.

Supporting Information



Publication History

Received: 24 August 2021

Accepted after revision: 23 September 2021

Accepted Manuscript online:
23 September 2021

Article published online:
03 November 2021

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
  • References

    • 1a Jiang CS, Müller WE. G, Schröder HC, Guo YW. Chem. Rev. 2012; 112: 2179
    • 1b Zhang H, Zou J, Yan X, Chen J, Cao X, Wu J, Liu Y, Wang T. Mar. Drugs 2021; 19: 180
    • 1c Prinsep MR. Studies in Natural Products Chemistry, Vol. 28. Atta-ur-Rahman Elsevier Science; Amsterdam: 2003: 617-751
    • 1d Jiménez C. Studies in Natural Products Chemistry, Vol. 25. Atta-ur-Rahman Elsevier Science; Amsterdam: 2001
    • 1e Cao X, Cao L, Zhang W, Lu R, Bian JS, Nie X. Pharmacol. Ther. 2020; 216: 107687
    • 1f Hai Y, Wei M.-Y, Wang C.-Y, Gu Y.-C, Shao C.-L. Marine Life Sci. Technol. 2021; 3: 488
    • 1g Xu J. RSC Adv. 2015; 5: 841
  • 2 Zhang FZ, Li XM, Yang SQ, Meng LH, Wang BG. J. Nat. Prod. 2019; 82: 1535
    • 3a Ghosh S, Kumar SU, Shashidhar J. J. Org. Chem. 2008; 73: 1582
    • 3b Ghosh S, Pradhan TK. J. Org. Chem. 2010; 75: 2107
    • 3c Athe S, Chandrasekhar B, Roy S, Pradhan TK, Ghosh S. J. Org. Chem. 2012; 77: 9840
    • 3d Reddy KM, Yamini V, Singarapu KK, Ghosh S. Org. Lett. 2014; 16: 2658
    • 3e Chandrasekhar B, Athe S, Reddy PP, Ghosh S. Org. Biomol. Chem. 2015; 13: 115
    • 3f Rao KN, Kanakaraju M, Kunwar AC, Ghosh S. Org. Lett. 2016; 18: 4092
    • 3g Athe S, Sharma A, Marumudi K, Ghosh S. Org. Biomol. Chem. 2016; 14: 6769
    • 3h Sharma A, Athe S, Ghosh S. ACS Omega 2018; 3: 16563
    • 4a Gradillas A, Castells JP. Angew. Chem. Int. Ed. 2006; 45: 6086
    • 4b Grubbs RH, Chang S. Tetrahedron 1998; 54: 4413
    • 4c Love JA. In Handbook of Metathesis . Grubbs RH. Wiley-VCH; Weinheim: 2003: 296-322
    • 4d Mohapatra DK, Reddy DP, Dash U, Yadav JS. Tetrahedron Lett. 2011; 52: 151
    • 4e Fürstner A. Angew. Chem. Int. Ed. 2000; 39: 3012
    • 4f Trnka TM, Grubbs RH. Acc. Chem. Res. 2001; 34: 18
    • 4g Lecourt C, Dhambri S, Allievi L, Sanogo Y, Zeghbib N, Othman RB, Lannou MI, Sorin G, Ardisson J. Nat. Prod. Rep. 2018; 35: 105
    • 4h Yu H, Li X, Jia Y, Zhang D, Xu T. Tetrahedron 2021; 91: 132240 ; and reference 17 cited therein
  • 5 Reddy DP, Zhang N, Yu Z, Wang Z, He Y. J. Org. Chem. 2017; 82: 11262
    • 6a Farley AJ, Sandford C, Dixon DJ. J. Am. Chem. Soc. 2015; 137: 15992
    • 6b Yang J, Farley AJ, Dixon DJ. Chem. Sci. 2017; 8: 606
    • 7a Neises B, Steglich W. Angew. Chem. Int. Ed. 1978; 17: 522
    • 7b Kalyankar KB, Das S. Synth. Commun. 2019; 50: 322
    • 8a Brown HC, Jadhav PK. J. Am. Chem. Soc. 1983; 105: 2092
    • 8b Reddy MV, Yucel AJ, Ramachandran PV. J. Org. Chem. 2001; 66: 2512
    • 8c Shelke AM, Rawat V, Suryavanshi G, Sudalai A. Tetrahedron: Asymmetry 2012; 23: 1534
    • 9a Kondo Y, Suzuki N, Takahashi M, Kumamoto T, Masu H, Ishikawa T. J. Org. Chem. 2012; 77: 7988
    • 9b Avi M, Gaisberger R, Feichtenhofer S, Griengl H. Tetrahedron 2009; 65: 5418
    • 9c Righi G, Pescatore G, Bonadies F, Bonini C. Tetrahedron 2001; 57: 5649
    • 10a Omura K, Swern D. Tetrahedron 1978; 34: 1651
    • 10b Mancusa AJ, Brownfain DS, Swern D. J. Org. Chem. 1979; 44: 4148
    • 11a Corey EJ, Venkateswarlu A. J. Am. Chem. Soc. 1972; 94: 6190
    • 11b Essig S, Bretzke S, Müller R, Menche D. J. Am. Chem. Soc. 2012; 134: 19362
    • 12a Singh AA, Zulkifli SN. A, Meyns M, Hayes PY, De Voss JJ. Tetrahedron: Asymmetry 2011; 22: 1709
    • 12b Eisenbraun EJ. Org. Synth. 1965; 45: 28
    • 13a Petit Y, Larchevêque M. Org. Synth. 1998; 75: 37
    • 13b Liu F, Mayer JP. J. Org. Chem. 2013; 78: 9848
    • 13c Ferko B, Zeman M, Formica M, Veselý S, Doháňošová J, Moncol J, Olejníková P, Berkeš D, Jakubec P, Dixon DJ, Ol’ga CO. J. Org. Chem. 2019; 84: 7159
  • 14 Ahmed F, Avery KL, Cullis PM, Primrose WU, Roberts GC. K, Al-Mutairi EH, Willi CL. Chem. Commun. 1999; 20: 2049