Synlett 2016; 27(01): 61-66
DOI: 10.1055/s-0035-1560814
letter
© Georg Thieme Verlag Stuttgart · New York

A Second-Generation Chemoenzymatic Total Synthesis of Platencin

Rehmani N. Muhammad
a   Research School of Chemistry, Institute of Advanced Studies, The Australian National University, Canberra, ACT 2601, Australia   Email: Martin.Banwell@anu.edu.au
,
Alistair G. Draffan
b   Biota Scientific Management Pty Ltd, Melbourne, VIC 3168, Australia
,
Martin G. Banwell*
a   Research School of Chemistry, Institute of Advanced Studies, The Australian National University, Canberra, ACT 2601, Australia   Email: Martin.Banwell@anu.edu.au
,
Anthony C. Willis
a   Research School of Chemistry, Institute of Advanced Studies, The Australian National University, Canberra, ACT 2601, Australia   Email: Martin.Banwell@anu.edu.au
› Author Affiliations
Further Information

Publication History

Received: 01 October 2015

Accepted after revision: 14 October 2015

Publication Date:
05 November 2015 (online)


Dedicated to Professor Steve Ley on the occasion of his 70th birthday and in appreciation of the inspirational leadership he has provided to the discipline

Abstract

A total synthesis of the potent antibacterial agent platencin is described. The reaction sequence used involves, as starting material, an enantiomerically pure cis-1,2-dihydrocatechol derived from the whole-cell biotransformation of iodobenzene. Simple chemical manipulations of this metabolite provide a triene that engages in a thermally promoted intramolecular Diels–Alder reaction to establish the octa­hydro-2H-2,4a-ethanonaphthalene core of platencin.

Supporting Information

 
  • References and Notes

    • 1a Hancock RE. W. Nat. Rev. Drug Discov. 2007; 6: 28
    • 1b Appelbaum PC. J. Antimicrob. Chemther. 2012; 67: 2062
    • 1c Shapiro S. J. Antibiot. 2013; 66: 371
    • 1d Tommasi R, Brown DG, Walkup GK, Manchester JI, Miller AA. Nat. Rev. Drug Discov. 2015; 14: 529
    • 2a Payne DJ, Gwynn MN, Holmes DJ, Pompliano DL. Nat. Rev. Drug Discov. 2007; 6: 29
    • 2b Lewis K. Nature (London, U.K.) 2012; 485: 439
    • 2c Lewis K. Nat. Rev. Drug Discov. 2013; 12: 3781
    • 2d Reardon S. Nature (London, U.K.) 2015; 521: 402
    • 2e Garber K. Nat. Rev. Drug Discov. 2015; 14: 445

      For some reviews, see:
    • 3a Tiefenbacher K, Mulzer J. Angew. Chem. Int. Ed. 2008; 47: 2548
    • 3b Palanichamy K, Kaliappan KP. Chem. Asian J. 2010; 5: 668
    • 3c Martens E, Deamin AL. J. Antibiot. 2011; 64: 705
    • 3d Saleem M, Hussain H, Ahmed I, van Ree T, Krohn K. Nat. Prod. Rep. 2011; 28: 1534
    • 3e Allahverdiyev AM, Bagirova M, Abamor ES, Ates SC, Koc RC, Miralogu M, Elcicek S, Yaman S, Unal G. Infect. Drug. Resist. 2013; 6: 99
  • 4 Parson JB, Yao J, Frank MW, Rock CO. Antimicrob. Agents Chemother. 2015; 59: 849 ; and references cited therein

    • See, for example:
    • 5a Leung GY. C, Li H, Toh Q.-Y, Ng AM.-Y, Sum RJ, Bandow JE, Chen DY.-K. Eur. J. Org. Chem. 2011; 183
    • 5b Plesch E, Bracher F, Krauss J. Arch. Pharm. 2012; 345: 657
    • 5c Krauss J, Plesch E, Clausen S, Bracher F. Sci. Pharm. 2014; 82: 501 ; and references cited therein
    • 6a Nicolaou KC, Tria GS, Edmonds DJ. Angew. Chem. Int. Ed. 2008; 47: 1780
    • 6b Nicolaou KC, Tria GS, Edmonds DJ, Kar M. J. Am. Chem. Soc. 2009; 131: 15909
  • 7 Austin KA. B, Banwell MG, Willis AC. Org. Lett. 2008; 10: 4465
  • 8 Tiefenbacher K, Mulzer J. J. Org. Chem. 2009; 74: 2937
  • 9 Chang EL, Schwartz BD, Draffan AG, Banwell MG, Willis AC. Chem. Asian J. 2015; 10: 427
    • 10a Moustafa GA. I, Saku Y, Aoyama H, Yoshimitsu T. Chem. Commun. 2014; 50: 15706
    • 10b Wang JW, Sun W.-B, Li YZ, Wang X, Sun B.-F, Lin G.-Q, Zou J.-P. Org. Chem. Front. 2015; 2: 674 ; and references cited therein

      For reviews on methods for generating cis-1,2-dihydrocatechols by microbial dihydroxylation of the corresponding aromatics, as well as the synthetic applications of these metabolites, see:
    • 11a Hudlicky T, Gonzalez D, Gibson DT. Aldrichimica Acta 1999; 32-35
    • 11b Banwell MG, Edwards AJ, Harfoot GJ, Jolliffe KA, McLeod MD, McRae KJ, Stewart SG, Voegtle M. Pure Appl. Chem. 2003; 75: 223
    • 11c Johnson RA. Org. React. 2004; 63: 117
    • 11d Hudlicky T, Reed JW. Synlett 2009; 685
    • 11e Bon DJ.-Y. D, Lee B, Banwell MG, Cade IA. Chim. Oggi 2012; 30: 22 ; Chiral Technologies Supplement
    • 11f Rinner U. Chiral Pool Synthesis: Chiral Pool Syntheses from cis-Cyclohexadiene Diols. In Comprehensive Chirality. Carreira EM, Yamamoto H. 2012, Vol. 2: 2, 40
  • 12 Entwistle DA, Hudlicky T. Tetrahedron Lett. 1995; 36: 2591
  • 13 For general procedures for the preparation of acetonides of this type, see: Hudlicky T, Boros EE, Olivo HF, Merola JS. J. Org. Chem. 1992; 57: 1026
  • 14 These types of acetonides are prone to dimerization: Ley SV, Redgrave AJ, Taylor SC, Ahmed S, Ribbons DW. Synlett 1991; 741
  • 15 Boyd DR, Sharma ND, Byrne B, Hand MV, Malone JF, Sheldrake GN, Blacker J, Dalton H. J. Chem. Soc., Perkin Trans. 1 1998; 1935

    • For some key earlier studies on the Diels–Alder cycloaddition reactions of cis-1,2-dihydrocatechol derivatives, see:
    • 16a First example, used for proof of structure: Gibson DT, Hensley M, Yoshioka H, Mabry TJ. Biochemistry 1970; 9: 1626
    • 16b First application in synthesis, singlet oxygen as dienophile: Hudlicky T, Luna H, Barbieri G, Kwart LD. J. Am. Chem. Soc. 1988; 110: 4735
    • 16c First IMDA reaction: Hudlicky T, Seoane G, Pettus T. J. Org. Chem. 1989; 54: 4239
    • 16d Downing W, Latouche R, Pittol CA, Pryce RJ, Roberts SM, Ryback G, Williams JO. J. Chem. Soc., Perkin Trans. 1 1990; 2613
    • 16e Mahon MF, Molloy K, Pittol CA, Pryce RJ, Roberts SM, Ryback G, Sik V, Williams JO, Winders JA. J. Chem. Soc., Perkin Trans. 1 1991; 1255
  • 17 Detailed experimental protocols for the synthesis of all new compounds and the spectroscopic data derived from them are provided in the Supporting Information.
  • 18 Nicolaou KC, Gray DL. F, Montagnon T, Harrison ST. Angew. Chem. Int. Ed. 2002; 41: 996
  • 19 Details of this X-ray analysis, including the derived ORTEP, are provided in the Supporting Information.
  • 20 This protocol is based on one first described by Ma and Bobbitt: Ma Z, Bobbitt JM. J. Org. Chem. 1991; 56: 6110
  • 21 Inokuchi T, Kawafuchi H, Torii S. Chem. Lett. 1992; 1895
  • 22 Procedure for the Reductive Deoxygenation of Compound 20 A solution of freshly prepared VCl3·(THF)3 23 (210 mg, 0.56 mmol) in dry toluene (2.5 mL) maintained at 18 °C was treated with freshly activated Zn dust (37 mg, 0.56 mmol) and the ensuing mixture irradiated in an ultrasonic bath (B2500R-DTH model from Branson) for 0.33 h. After this time a solution of acetate 20 (109 mg, 0.28 mmol) in toluene (1.5 mL) was added and sonication continued for 0.66 h. The reaction mixture was then diluted with EtOAc (5.0 mL) and passed through a short plug of TLC-grade silica gel that was washed with EtOAc (3 × 5 mL). The combined filtrates were washed with H2O (1 × 10 mL) before being dried (MgSO4), filtered, and concentrated under reduced pressure. The resulting light-yellow oil was subjected to flash chromatography (silica, 1:4 v/v EtOAc–hexane elution) to afford, after concentration of the relevant fractions (Rf  = 0.4), compound 21 5a (75 mg, 81%) as a white foam. A full spectroscopic data set for this compound is provided in the Supporting Information.
  • 23 Manzer LE. Inorg. Synth. 1982; 21: 135
  • 24 Smanski MJ, Yu Z, Casper J, Lin S, Peterson RM, Chen Y, Wendt-Pienkowski E, Rajski SR, Shen B. Proc. Natl. Acad. Sci., U.S.A. 2011; 108: 13498