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Synlett 2012; 23(10): 1493-1496
DOI: 10.1055/s-0031-1290675
DOI: 10.1055/s-0031-1290675
letter
Toward a New Palmerolide Assembly Strategy: Synthesis of C16–C24
Further Information
Publication History
Received: 16 February 2012
Accepted after revision: 02 April 2012
Publication Date:
29 May 2012 (online)
![](https://www.thieme-connect.de/media/synlett/201210/lookinside/thumbnails/10.1055-s-0031-1290675-1.jpg)
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.
Key words
palmerolide - stereoselective synthesis - coupling - natural products - asymmetric catalysisSupporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
Primary Data
- for this article are available online at http://www.thieme-connect.com/ejournals/toc/synlett and can be cited using the following DOI: 10.4125/pd0029th
- Primary Dat
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References and Notes
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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
Total syntheses:
Formal syntheses:
Synthetic approaches: