Total Synthesis of 8-Methoxygoniodiol via Chiron Approach

J. S. Yadav; B. Madhava Rao; K. Sanjeevarao; B. V. Subba Reddy

doi:10.1055/s-2008-1072511

LETTER

Total Synthesis of 8-Methoxygoniodiol via Chiron Approach

J. S. Yadav*, B. Madhava Rao, K. Sanjeevarao, B. V. Subba Reddy
Division of Organic Chemistry, Indian Institute of Chemical Technology, Hyderabad 500 007, India
Fax: +91(40)27160512; e-Mail: yadav@iict.res.in;

Abstract

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Abstract

A stereoselective synthesis of 8-methoxygoniodiol is accomplished using readily available δ-gluconolactone as a chiral source. The stereoselective addition of aryl Grignard reagent on aldehyde and regioselective opening of chiral epoxide by ethyl propiolate are the key steps involved in this synthesis.

Keywords

goniodiol - δ-gluconolactone - chiron approach - chiral epoxide

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References

References and Notes

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15

Compound 6: [α]_D ²⁵ +15.8 (c 1.0, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 1.41, 1.37, 1.34, 1.32 (4 s, 12 H), 3.90-4.20 (m, 5 H), 4.25 (d, J = 4.6 Hz, 1 H), 7.3 (m, 5 H). ¹³C NMR (75 MHz, CDCl₃): δ = 25.1, 26.3, 26.6, 27.1, 72.6, 75.4, 76.7, 82.6, 83.6, 109.0, 110.0, 126.8, 127.74, 128.5, 140.0. IR (KBr): ν_max = 3438, 2990, 2874, 1376, 1153, 1070, 843, 702 cm^-1. HRMS: m/z calcd for C₁₇H₂₄O₅ [M + Na]⁺: 331.1521; found: 331.1512.
Compound 8: [α]_D ²⁵ +67.6 (c 0.5, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 1.41, 1.37, 1.34, 1.32 (4 s, 12 H), 3.23 (s, 3 H), 3.94-4.15 (m, 5 H), 4.25 (d, J = 4.5 Hz, 1 H), 7.13 (m, 5 H). ¹³C NMR (75 MHz, CDCl₃): δ = 25.1, 26.3, 26.5, 27.2, 56.4, 72.3, 75.4, 76.6, 82.5, 83.4, 109.0, 110.0, 126.0, 127.7, 128.5, 138.5. IR (KBr): ν_max = 2987, 1456, 1372, 1214, 1076, 848, 706 cm^-1. HRMS: m/z calcd for C₁₈H₂₆O₅ [M + Na]⁺: 345.1676; found: 345.1669.
Compound 10: [α]_D ²⁵ +37.2 (c 1.7, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 1.26 (s, 3 H), 1.39 (s, 3 H), 2.85 (m, 1 H), 3.12 (dd, J = 3.0, 3.7 Hz, 1 H), 3.30 (s, 3 H), 3.70 (m, 1 H), 4.05 (dd, J = 6.7, 8.3 Hz, 1 H), 4.25 (d, J = 6.7 Hz, 1 H), 7.25-7.36 (m, 5 H). ¹³C NMR (75 MHz, CDCl₃): δ = 26.0, 29.0, 56.0, 62.0, 78.0, 79.0, 85.0, 109.0, 127.0, 128.0, 136.0. IR (KBr): ν_max = 3462, 2987, 1455, 1375, 1097, 860, 705
cm^-1. HRMS: m/z calcd for C₁₄H₂₀O₄ [M + Na]⁺: 275.1259; found: 175.1250.
Compound 12: [α]_D ²⁵ +37.9 (c 2.9, CHCl₃) ¹H NMR (300 MHz, CDCl₃): δ = 2.48-2.54 (m, 2 H), 2.70 (dd, J = 3.0, 3.7 Hz 1 H), 3.27 (s, 3 H), 3.65 (dd, J = 2.2, 7.5 Hz, 1 H), 4.17 (d, J = 7.5 Hz, 1 H), 7.30 (m, 5 H). ¹³C NMR (75 MHz, CDCl₃): δ = 45.0, 52.0, 57.0, 75.0, 86.0, 127.0, 128.0, 129.0, 138.0. IR (KBr): ν_max = 3424, 2927, 1724, 1453, 1102, 760, 701 cm^-1. HRMS: m/z calcd for C₁₁H₁₄O₃ [M + Na]⁺: 217.0840; found: m/z 217.0843.
Compound 14: [α]_D ²⁵ +61.0 (c 1.4, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 0.16 (s, 3 H), 0.18 (s, 3 H), 0.93 (s, 9 H), 1.29 (t, J = 7.0 Hz, 3 H), 2.40 (dd, J = 3.1, 6.2 Hz, 2 H), 3.12 (s, 3 H), 3.25 (m, 1 H), 3.89 (d, J = 7.8 Hz, 1 H), 4.11 (d, J = 7.8 Hz, 1 H), 4.18 (q, J = 7.0 Hz, 2 H), 7.30 (m, 5 H). ¹³C NMR (75 MHz, CDCl₃): δ = -4.9, -3.7, 14.0, 25.1, 26.2, 29.7, 56.3, 61.8, 68.7, 76.6, 85.3, 85.8, 127.8, 128.3, 128.6, 138.1, 150.4. IR (KBr): ν_max = 3423, 3300, 2927, 1742, 1458, 1105, 760 cm^-1. LC-MS: m/z = 429 [M + Na]⁺.
Compound 1: [α]_D ²⁵ +24.9 (c 0.35, CHCl₃); lit.: +24.2 (c 0.68, CDCl₃. ¹H NMR (300 MHz, CDCl₃): δ = 2.04 (ddd, J = 4.0, 6.2, 18.5 Hz, 1 H), 2.94 (ddd, J = 2.4, 13.0, 18.5 Hz, 1 H), 3.27 (s, 3 H), 3.56 (d, J = 8.5 Hz, 1 H), 3.92 (ddd, J = 3.9, 12.5, 17.9 Hz, 1 H), 4.55 (d, J = 8.5 Hz, 1 H), 5.93 (dd, J = 3.1, 10.2 Hz, 1 H), 6.82 (ddd, J = 2.3, 6.2, 9.4 Hz, 1 H), 7.30-7.39 (m, 5 H). ¹³C NMR (75 MHz, CDCl₃): δ = 25.8, 56.8, 61.8, 75.7, 75.8, 83.4, 120.7, 127.7, 128.6, 128.7, 137.3, 145.7, 163.8. IR (KBr): ν_max = 3445, 2909, 1719, 1380, 1109, 1057, 757 cm^-1. HRMS: m/z calcd for C₁₄H₁₆O₄ [M + Na]⁺: 271.0946; found: 271.0945.