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Synlett 2013; 24(20): 2679-2682
DOI: 10.1055/s-0033-1339896
DOI: 10.1055/s-0033-1339896
letter
A Carbohydrate-Based Approach for the Total Synthesis of Xyolide
Further Information
Publication History
Received: 16 August 2013
Accepted after revision: 05 September 2013
Publication Date:
28 October 2013 (online)
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Abstract
We have achieved a total synthesis of xyolide, a bioactive nonenolide, by following a carbohydrate-based approach starting from d-(–)-ribose. The key reactions involved epoxide opening with a long-chain aliphatic Grignard reagent, Yamaguchi esterification, and a ring-closing-metathesis reaction. The longest linear sequence was nine steps and the overall yield was 30%.
Key words
lactones - total synthesis - Grignard reactions - esterification - ring closure - metathesisSupporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
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References and Notes
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- 21 Analytical Data for 12: [α]D 27 +22.6 (c 1.5, CHCl3). IR (neat): 3081, 2929, 2858, 1740, 1464, 1377, 1253, 1215, 1167, 1122, 1074, 925, 838, 725 cm–1. 1H NMR (300 MHz, CDCl3): δ = 5.86–5.70 (m, 2 H), 5.37–5.03 (m, 4 H), 4.91 (dt, J = 3.4, 7.4 Hz, 1 H), 4.6 (t, J = 7.2 Hz, 1 H), 4.22–4.13 (m, 2 H), 2.34–2.25 (m, 2 H), 1.83–1.37 (m, 2 H), 1.48 (s, 3 H), 1.37 (s, 3 H), 1.34–1.22 (m, 12 H), 0.91 (s, 9 H), 0.88 (t, J = 7.0 Hz, 3 H), 0.51 (s, 3 H), 0.32 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 172.6, 140.6, 133.2, 118.3, 114.3, 108.6, 78.8, 78.3, 72.3, 71.7, 32.5, 31.7, 31.1, 29.6, 29.4, 29.1, 27.4, 25.7, 25.1, 24.4, 22.5, 18.1, 14.0, −4.5, −4.9. MS (ESI): m/z = 505 [M + Na]+.
- 22 Analytical Data for 11: [α]D 27 +28.8 (c 2.1, CHCl3). IR (neat): 3474, 3083, 2957, 2928, 2858, 1739, 1459, 1427, 1380, 1250, 1216, 1067, 993, 927, 874 cm–1. 1H NMR (300 MHz, CDCl3): δ = 5.90–5.76 (m, 2 H), 5.37–5.12 (m, 4 H), 4.92 (dt, J = 3.4, 7.6 Hz, 1 H), 4.61 (m, 1 H), 4.21–4.15 (m, 2 H), 2.47–2.32 (m, 2 H), 1.92–1.84 (m, 2 H), 1.81 (m, 1 H), 1.69 (m, 1 H), 1.48 (s, 3 H), 1.37 (s, 3 H), 1.31–1.23 (m, 10 H), 0.87 (t, J = 6.7 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 172.8, 140.3, 133.0, 118.4, 115.0, 108.7, 78.7, 78.2, 72.0, 71.9, 31.7, 31.4, 31.0, 30.2, 29.4, 29.0, 27.4, 25.1, 24.5, 22.5, 14.0. MS (ESI): m/z = 391 [M + Na]+.
- 23 Analytical Data for 10: [α]D 27 +47.2 (c 0.7, CHCl3). IR (neat): 3484, 3082, 2956, 2928, 2858, 1737, 1459, 1378, 1166, 1065, 927, 874 cm–1. 1H NMR (300 MHz, CDCl3): δ = 5.81 (dd, J = 3.3, 15.8 Hz, 1 H), 5.65 (ddd, J = 1.8, 8.7, 15.8 Hz, 1 H), 4.92 (m, 1 H), 4.68 (m, 1 H), 4.16 (m, 1 H), 3.96 (q, J = 4.7, 10.0 Hz, 1 H), 2.34 (m, 1 H), 2.11–2.01 (m, 2 H), 1.78 (m, 1 H), 1.64 (m, 1 H), 1.46 (m, 1 H), 1.54 (s, 3 H), 1.37 (s, 3 H), 1.32–1.20 (m, 10 H), 0.86 (t, J = 6.7 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 175.0, 128.1, 126.2, 109.2, 78.4, 75.5, 75.5, 70.8, 33.5, 31.8, 31.6, 31.1, 29.2, 29.0, 28.3, 26.1, 24.3, 22.5, 13.9. MS (ESI): m/z = 363 [M + Na]+.
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- 25 Analytical Data for Xyolide (1): [α]D 27 +2.6 (c 1.2, CHCl3). IR (neat): 3613, 3497, 3044, 1744, 1694, 1377, 1059, 968, 772 cm–1. 1H NMR (500 MHz, CDCl3): δ = 5.86 (dd, J = 1.4, 15.8 Hz, 1 H), 5.49 (ddd, J = 1.7, 9.3, 15.8 Hz, 1 H), 5.14 (m, 1 H), 4.99 (td, J = 2.2, 9.6 Hz, 1 H), 4.50 (br s, J = 1.3, 1.9 Hz, 1 H), 3.56 (dd, J = 1.9, 9.6 Hz, 1 H), 2.67–2.62 (m, 2 H), 2.61–2.51 (m, 2 H), 2.37–2.31 (m, 1 H), 2.09–1.96 (m, 3 H), 1.92–1.83 (m, 1 H), 1.59–1.49 (m, 1 H), 1.33–1.20 (m, 10 H), 0.87 (t, J = 6.7 Hz, 3 H). 13C NMR (125 MHz, CDCl3): δ = 176.1, 174.5, 171.60, 132.7, 123.4, 76.4, 73.1, 72.4, 70.8, 31.7, 31.4, 31.2, 29.5, 29.4, 29.3, 29.1, 28.8, 24.5, 22.6, 14.0. MS (ESI): m/z = 423 [M + Na]+, 399 [M − H]+.
For a review on synthetic, biosynthetic, and pharmacological aspects of decanolides, see: