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

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  • 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