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

doi:10.1055/s-2007-967970

LETTER

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;

Abstract

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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

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References

References and Notes

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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.

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.

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.

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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.

The crystallo-graphic data for 20 has been deposited at the Cambridge Crystallographic Data Centre with deposition no. CCDC 632316.

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.

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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.