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Synlett 2007(4): 0571-0574  
DOI: 10.1055/s-2007-967970
LETTER
© Georg Thieme Verlag Stuttgart · New York

Asymmetric Synthesis of the Diene Unit of Methyl Sartortuoate via a Temperature-Sensitive Intramolecular Horner-Wadsworth-Emmons (HWE) Reaction

Hequan Yao, Yuan Gao, Peng Liu, Bingfeng Sun, Xingxiang Xu*
Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, P. R. of China
Fax: +86(21)64166128; e-Mail: xuxx@mail.sioc.ac.cn;
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Publication History

Received 15 November 2006
Publication Date:
21 February 2007 (online)

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Abstract

The asymmetric synthesis of the diene unit of methyl ­sartortuoate is described. A temperature-sensitive intramolecular Horner-Wadsworth-Emmons reaction was employed for the construction of the 14-membered ring. A Payne rearrangement of an 2,3-epoxy alcohol was utilized for the installation of the hydroxyl group at the C14 position of the diene unit.

Key words

asymmetric synthesis - methyl sartortuoate - diene unit - HWE reaction - Payne rearrangement

    References and Notes

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    Compound 20: white solid; mp 80-81 °C; [α]D 20 -234 (c = 0.40, CHCl3). IR (film): 2942, 1740, 1376, 1243, 1092, 1033 cm-1. 1H NMR (300 MHz, CDCl3): δ = 6.27 (d, J = 10.5 Hz, 1 H), 6.05 (dd, J = 8.4 Hz, 2 H), 4.22 (d, J = 7.5 Hz, 1 H), 4.83 (d, J = 7.5 Hz, 1 H), 4.71 (d, J = 7.5 Hz, 1 H), 4.65 (d, J = 12.3 Hz, 1 H), 4.37 (d, J = 12.3 Hz, 1 H), 4.92 (d, J = 7.5 Hz, 1 H), 3.97-4.01 (m, 1 H), 3.73 (d, J = 8.4 Hz, 1 H), 3.40 (s, 3 H), 3.32 (s, 3 H), 2.50-2.62 (m, 1 H), 2.15-2.33 (m, 1 H), 2.14-2.15 (m, 8 H), 2.054 (s, 3 H), 2.047 (s, 3 H), 1.74 (s, 3 H), 1.23 (s, 3 H), 1.21 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 170.6, 170.1, 139.0, 134.6, 126.0, 118.1, 91.0, 90.8, 82.7, 79.9, 75.2, 69.0, 68.4, 65.2, 55.7, 55.2, 40.4, 39.8, 30.3, 24.6, 21.1 (2 C), 21.0, 20.0, 19.9, 18.3. ESI-MS: m/z = 521.3 [M + Na]+. HRMS (ESI): m/z [M + Na]+ calcd for C26H42O9: 521.2721; found: 521.2743.

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10

Compound 15: colorless oil; [α]D 20 +15.8 (c = 0.50, MeOH). IR (film): 2932, 1717, 1676, 1448, 1184, 1137, 1098, 1037 cm-1. 1H NMR (300 MHz, CDCl3): δ = 10.09 (d, J = 7.8 Hz, 1 H), 6.14 (s, 1 H), 6.12 (d, J = 7.8 Hz, 1 H), 5.39 (s, 1 H), 5.22 (t, J = 7.5 Hz, 1 H), 4.77 (d, J = 7.2 Hz, 1 H), 4.72 (d, J = 7.2 Hz, 1 H), 4.22 (q, J = 7.2 Hz, 2 H), 4.08-4.11 (m, 1 H), 3.62-3.66 (m, 1 H), 3.39 (s, 3 H), 3.01 (d, J = 7.5 Hz, 2 H), 2.19 (s, 3 H), 1.40-2.10 (m, 8 H), 1.64 (s, 3 H), 1.30 (t, J = 7.2 Hz, 3 H), 1.20 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 191.7, 167.3, 161.6, 139.7, 137.2, 126.2, 124.4, 120.8, 90.7, 77.8, 74.8, 72.67, 60.6, 55.5, 36.0, 31.5, 30.1, 26.5, 24.6, 21.0, 16.1, 14.3, 14.2. ESI-MS: m/z = 409.1 [M + H]+, 431.1 [M + Na]+. HRMS (ESI): m/z [M + Na]+ calcd for C23H36O6: 431.2404; found: 431.2401.

11

Compound 8: colorless oil; [α]D 20 +88.4 (c = 0.49, CHCl3). IR (film): 2979, 2934, 1707, 1448, 1380, 1222, 1145, 1097, 1037, 919 cm-1. 1H NMR (300 MHz, CDCl3): δ = 6.81 (t, J = 7.2 Hz, 1 H), 5.36 (t, J = 7.5 Hz, 1 H), 4.82 (d, J = 8.1 Hz, 1 H), 4.77 (d, J = 7.5 Hz, 1 H), 4.75 (d, J = 7.5 Hz, 1 H), 4.73 (d, J = 8.1 Hz, 1 H), 4.22 (q, J = 7.2 Hz, 2 H), 3.76-3.80 (m, 1 H), 3.69 (d, J = 5.1 Hz, 1 H), 3.38 (s, 3 H), 3.37 (s, 3 H), 2.70-3.10 (m, 4 H), 2.32-2.40 (m, 1 H), 2.00-2.10 (m, 2 H), 1.80-2.00 (m, 2 H), 1.50-1.70 (m, 3 H), 1.62 (s, 3 H), 1.32 (t, J = 7.2 Hz, 3 H), 1.25 (s, 3 H), 1.19 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 168.0, 142.0, 139.1, 127.8, 123.2, 91.4, 90.9, 79.6, 77.4, 76.4, 75.9, 60.0, 55.6, 55.4, 39.7, 38.4, 33.9, 29.5, 27.7, 23.6, 22.7, 21.4, 15.4, 14.3. ESI-MS: m/z = 463.2 [M + Na]+. HRMS (ESI): m/z [M + Na]+ calcd for C24H40O7: 463.2666; found: 463.2685.

12

The stereochemistry of the conjugated double bond is assigned from the chemical shift and the coupling constant data of the vinylic proton, and by analogy with closely related cyclizations.

18

Compound 22: colorless oil; [α]D 20 -254 (c = 0.10, CHCl3). IR (film): 2981, 2945, 2855, 1734, 1673, 1647, 1440, 1376, 1275, 1244, 1033, 910 cm-1. 1H NMR (300 MHz, CDCl3): δ = 6.98 (d, J = 10.2Hz, 1 H), 6.25 (d, J = 11.1 Hz, 1 H), 5.95 (d, J = 10.2 Hz, 1 H), 5.03 (d, J = 7.2 Hz, 1 H), 4.82 (d, J = 7.5 Hz, 1 H), 4.69 (d, J = 7.5 Hz, 1 H), 4.42 (d, J = 7.2 Hz, 1 H), 3.98-4.02 (m, 1 H), 3.70-3.73 (m, 1 H), 3.40 (s, 3 H), 3.33 (s, 3 H), 1.80-2.70 (m, 4 H), 2.27 (s, 3 H), 2.00 (s, 3 H), 1.40-1.80 (m, 6 H), 1.83 (s, 3 H), 1.23 (s, 3 H), 1.20 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 190.2, 170.6, 145.2, 140.7, 131.9, 118.3, 91.1, 91.0, 82.5, 80.1, 75.2, 68.5, 68.4, 55.7, 55.3, 40.2, 39.6, 30.1, 27.5, 24.5, 21.3, 21.0, 20.1, 20.0, 18.8. ESI-MS: m/z = 491.1 [M + Na+]. HRMS (ESI): m/z [M + Na]+ calcd for C25H40O8: 491.2615; found: 491.2605.

22

Compound 5: colorless oil; [α]D 20 -176 (c = 0.05, CHCl3). IR (film): 2925, 2853, 1742, 1458, 1375, 1240, 1144, 1092, 1072, 1034, 910 cm-1. 1H NMR (500 MHz, CDCl3): δ = 6.08-6.13 (m, 3 H), 4.96 (d, J = 7.4 Hz, 1 H), 4.93 (s, 1 H), 4.85 (s, 1 H), 4.84 (d, J = 7.3 Hz, 1 H), 5.03 (d, J = 7.3 Hz, 1 H), 4.39 (d, J = 7.4 Hz, 1 H), 4.03 (dd, J = 3.0 Hz, 1 H), 3.69 (d, J = 8.3 Hz, 1 H), 3.40 (s, 3 H), 3.33 (s, 3 H), 1.40-2.80 (m, 10 H), 1.98 (s, 3 H), 1.88 (s, 3 H), 1.73 (s, 3 H), 1.25 (s, 3 H), 1.21 (s, 3 H). 13C NMR (125 MHz, CDCl3): δ = 169.9, 143.5, 137.4, 121.2, 119.0, 113.9, 112.9, 91.1, 91.0, 82.7, 80.2, 75.3, 69.8, 68.3, 55.7, 55.2, 40.3, 39.8, 30.4, 29.7, 24.6, 22.8, 21.5, 21.1, 20.2, 18.4. ESI-MS: m/z = 489.4 [M + Na]+. HRMS (ESI): m/z [M + Na]+ calcd for C26H42O7: 489.2828; found: 489.2823.