Synlett 2012; 23(10): 1493-1496
DOI: 10.1055/s-0031-1290675
letter
© Georg Thieme Verlag Stuttgart · New York

Toward a New Palmerolide Assembly Strategy: Synthesis of C16–C24

Marilda P. Lisboa
,
Jeannie H. Jeong-Im
,
David M. Jones
,
Gregory B. Dudley*
Further Information

Publication History

Received: 16 February 2012

Accepted after revision: 02 April 2012

Publication Date:
29 May 2012 (online)


Abstract

Asymmetric synthesis of C16–C24 of palmerolide A is described, featuring convergent Negishi coupling, Singaram propargylation, and successful tactical maneuvering to address an unexpected allylic substitution reaction.

Supporting Information

Primary Data

 
  • References and Notes

  • 1 Current address: Department of Chemistry, University of Pennsylvania, Philadelphia, PA, USA

    • Total syntheses:
    • 2a Jiang X, Liu B, Lebreton S, De Brabander JK. J. Am. Chem. Soc. 2007; 129: 6386
    • 2b Nicolaou KC, Guduru R, Sun Y.-P, Banerji B, Chen DY.-K. Angew. Chem. Int. Ed. 2007; 46: 5896
    • 2c Penner M, Rauniyar V, Kaspar LT, Hall DG. J. Am. Chem. Soc. 2009; 131: 14216

      Formal syntheses:
    • 3a Jaegel J, Maier ME. Synthesis 2009; 2881
    • 3b Gowrisankar P, Pujari SA, Kaliappan KP. Chem. Eur. J. 2010; 16: 5858
    • 3c Prasad KR, Pawar AB. Org. Lett. 2011; 13: 4252
    • 3d Pujari SA, Gowrisankar P, Kaliappan KP. Chem. Asian J. 2011; 6: 3137
  • 5 In addition to the geographical barriers to harvesting in Antarctica, the Antarctic Treaty prohibits exploitation of South Pole resources for commercial gain. Information available through the Antarctic Treaty Secretariat: http://www.ats.aq
    • 6a Diyabalange T, Amsler CD, McClintock JB, Baker BJ. J. Am. Chem. Soc. 2006; 128: 5630
    • 6b Lebar MD, Baker BJ. Tetrahedron Lett. 2007; 48: 8009
    • 6c Riesenfeld CS, Murray AE, Baker BJ. J. Nat. Prod. 2008; 71: 1812
  • 7 Noguez JH, Diyabalanage TK. K, Miyata Y, Xie X.-S, Valeriote FA, Amsler CD, McClintock JB, Baker BJ. Bioorg. Med. Chem. 2011; 19: 6608
    • 8a Nicolaou KC, Sun Y.-P, Guduru R, Banerji B, Chen DY.-K. J. Am. Chem. Soc. 2008; 130: 3633
    • 8b Nicolaou KC, Leung GY. C, Dethe DH, Guduru R, Sun Y.-P, Lim CS, Chen DY.-K. J. Am. Chem. Soc. 2008; 130: 10019
    • 8c Ravu VR, Leung GY. C, Lim CS, Ng SY, Sum RJ, Chen DY.-K. Eur. J. Org. Chem. 2011; 463
    • 9a Kinghorn AD, Chin Y.-W, Swanson SM. Curr. Opin. Drug Discov. Devel. 2009; 12: 189
    • 9b Dalby SM, Paterson I. Curr. Opin. Drug Discov. Devel. 2010; 13: 777
    • 10a Kamijo S, Dudley GB. J. Am. Chem. Soc. 2005; 127: 5028
    • 10b Kamijo S, Dudley GB. Org. Lett. 2006; 8: 175
    • 10c Jones DM, Kamijo S, Dudley GB. Synlett 2006; 936
    • 10d Kamijo S, Dudley GB. J. Am. Chem. Soc. 2006; 128: 6499
    • 10e Kamijo S, Dudley GB. Tetrahedron Lett. 2006; 47: 5629
    • 10f Tummatorn J, Dudley GB. J. Am. Chem. Soc. 2008; 130: 5050
    • 10g Jones DM, Lisboa MP, Kamijo S, Dudley GB. J. Org. Chem. 2010; 75: 3260
    • 10h Jones DM, Dudley GB. Tetrahedron 2010; 66: 4860
    • 10i Tummatorn J, Dudley GB. Org. Lett. 2011; 13: 158
    • 10j Tummatorn J, Dudley GB. Org. Lett. 2011; 13: 1572
    • 10k Lisboa MP, Hoang TT, Dudley GB. Org. Synth. 2011; 88: 353
  • 11 King AO, Okukado N, Negishi EI. J. Chem. Soc., Chem. Commun. 1977; 683
  • 12 Cheon C.-G, Kim W.-S, Smith AB. III. Org. Lett. 2005; 7: 3569
  • 13 Sun B, Xu X. Tetrahedron Lett. 2005; 46: 8431
  • 14 Eliel EL, Wilen SH, Mander LN. Stereochemistry of Organic Compounds. John Wiley and Sons; New York, NY: 1994
    • 15a Hirayama LC, Dunham KK, Singaram B. Tetrahedron Lett. 2006; 47: 5173
    • 15b For previous application in synthesis, see: Francais A, Leyva A, Etxebarria-J G, Ley SV. Org. Lett. 2010; 12: 340
    • 16a Van Horn DE, Negishi E. J. Am. Chem. Soc. 1978; 100: 2252
    • 16b Wipf P, Lim S. Angew. Chem., Int. Ed. Engl. 1993; 32: 1068
    • 17a Kallan NC, Halcomb RL. Org. Lett. 2000; 2: 2687
    • 17b Romero-Ortega M, Colby DA, Olivo HF. Tetrahedron Lett. 2002; 43: 6439
    • 17c Quéron E, Lett R. Tetrahedron Lett. 2004; 45: 4527
  • 18 Procedure and Data for C16–C24 Fragment 2 To a solution of vinyl iodide 14 (20 mg, 0.062 mmol) in CH2Cl2 (3 mL) was added imidazole (8 mg, 0.12 mmol) and TBSCl (11 mg, 0.074 mmol) at r.t. The reaction mixture was stirred overnight and quenched with NH4Cl. The solution was extracted with CH2Cl2 (3×) and the solvent evaporated under reduced pressure. The residue was purified by flash column chromatography on silica gel (EtOAc–hexanes = 5:95) to yield vinyl iodide 2 as a colorless oil (23 mg, 85%). [α]D 25 15.9 (c 5.32, CH2Cl2). IR (thin film): 3467 (br), 2954, 2928, 2856, 1462, 1379, 1252, 1050, 832, 773, 666 cm–1. 1H NMR (400 MHz, CDCl3): δ = 6.00 (d, J = 7.3 Hz, 1 H), 5.32–5.36 (m, 1 H), 4.19 (d, J = 6.2 Hz, 2 H), 3.62–3.68 (m, 1 H), 2.28–2.40 (m, 2 H), 2.12–2.20 (m, 1 H), 1.86 (d, J = 0.9 Hz, 3 H), 1.68–1.78 (m, 2 H), 1.60 (s, 3 H), 1.47 (d, J = 4.1 Hz, 2 H), 0.89 (s, 9 H), 0.84 (d, J = 6.8 Hz, 3 H), 0.06 (s, 6 H). 13C NMR (100 MHz, CDCl3): δ = 145.3, 135.1, 126.6, 71.3, 60.1, 44.7, 43.5, 35.5, 25.9, 24.0, 18.4, 16.1, 13.3, –5.1. ESI-HRMS: m/z calcd for C18H35O2ISiNa [M + Na+]: 461.1348; found: 461.1343