Total Synthesis of (+)-Guaymasol

Sophie Feuillastre; Olivier Piva

doi:10.1055/s-0034-1379480

Synlett, Table of Contents

Synlett 2014; 25(20): 2883-2886
DOI: 10.1055/s-0034-1379480

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Total Synthesis of (+)-Guaymasol

Sophie Feuillastre

Université de Lyon, Université Lyon 1, Institut de Chimie et de Biochimie Moléculaire et Supramoléculaire (ICBMS), UMR 5246 CNRS, Bat Raulin, 43, Bd du 11 novembre 1918, 69622 Villeurbanne cedex, France Fax: +33(4)72448136 Email: piva@univ-lyon1.fr

,

Olivier Piva*

Université de Lyon, Université Lyon 1, Institut de Chimie et de Biochimie Moléculaire et Supramoléculaire (ICBMS), UMR 5246 CNRS, Bat Raulin, 43, Bd du 11 novembre 1918, 69622 Villeurbanne cedex, France Fax: +33(4)72448136 Email: piva@univ-lyon1.fr

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Abstract

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Abstract

The synthesis of (+)-guaymasol has been achieved from O-methyl chavicol by using a sequence combining a cross-metathesis and an asymmetric dihydroxylation of the newly created double bond. The first step using Grubbs type II catalyst delivered an inseparable 88:12 mixture of E and Z isomers. After treatment with AD-mix-β and deprotection of the benzyl ether by hydrogenolysis, (+)-guaymasol was finally isolated in 84% de and 90% ee.

Key words

natural products - total synthesis - cross-metathesis - dihydroxylation - phenols

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References

References and Notes
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27 Selected data: Compound 12a: Yield: 56% (104 mg from 500 mg of 5a over 3 steps); colourless oil. 1 H NMR (300 MHz, CDCl₃): δ = 0.89 (d, J = 6.6 Hz, 6 H), 1.54–1.75 (m, 1 H), 1.91 (t, J = 6.2 Hz, 2 H), 3.28 (d, J = 6.2 Hz, 2 H), 5.05 (s, 2 H), 5.38–5.62 (m, 2 H), 6.91 (d, J = 8.6 Hz, 2 H), 7.10 (d, J = 8.6 Hz, 2 H), 7.28–7.46 (m, 5 H). ¹³C NMR (100 MHz, CDCl₃): δ = 22.5, 28.6, 38.4, 42.0, 70.2, 114.9, 127.6, 128.0, 128.7, 129.5, 130.4, 130.6, 133.7, 137.4, 157.2. HRMS (CI): m/z [M + H]⁺ calcd for C₂₀H₂₄O: 281.1900; found: 281.1902. Compound 12b: Yield: 8% (14 mg from 500 mg of 5a); colourless oil. ¹H NMR (300 MHz, CDCl₃): δ = 0.94 (d, J = 6.6 Hz, 6 H), 1.60–1.75 (m, 1 H), 2.04 (t, J = 6.7 Hz, 2 H), 3.34 (d, J = 6.7 Hz, 2 H), 5.05 (s, 2 H), 5.41–5.67 (m, 2 H), 6.92 (d, J = 8.5 Hz, 2 H), 7.11 (d, J = 8.6 Hz, 2 H), 7.28–7.48 (m, 5 H). Compound (+)-13a: Yield: 85% (100 mg from 118 mg of 12a/12b); white solid; mp 81–83 °C; [α]_D +18.1 (c = 0.5, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 0.94 (d, J = 6.8 Hz, 3 H), 0.92 (d, J = 6.8 Hz, 3 H), 1.20–1.38 (m, 2 H), 1.40–1.59 (m, 1 H), 1.66–1.90 (m, 2 H, OH), 2.67 (dd, J = 13.8, 8.5 Hz, 1 H), 2.85 (dd, J = 13.8, 3.9 Hz, 1 H), 3.51–3.70 (m, 2 H), 5.05 (s, 2 H), 6.94 (d, J = 8.6 Hz, 2 H), 7.15 (d, J = 8.6 Hz, 2 H), 7.26–7.48 (m, 5 H). ¹³C NMR (100 MHz, CDCl₃): δ = 22.0, 23.8, 24.7, 39.5, 43.0, 70.2, 71.8, 75.6, 115.2, 127.6, 128.1, 128.7, 130.4, 130.5, 137.2, 157.7. HRMS (ESI): m/z [M + Na] calcd for C₂₀H₂₆NaO₃: 337.1774; found: 337.1769. Compound rac-13b: Yield: 6% (9 mg from 100 mg of 5b); white solid; mp 81–83 °C. ¹H NMR (300 MHz, CDCl₃): δ = 0.94 (d, J = 6.5 Hz, 3 H), 0.99 (d, J = 6.7 Hz, 3 H), 1.14–1.38 (m, 2 H), 1.41–1.60 (m, 1 H), 1.66–1.96 (m, 2 H), 2.66 (dd, J = 13.9, 9.6 Hz, 1 H), 2.79 (dd, J = 3.5, 13.9 Hz, 1 H), 3.69–3.87 (m, 2 H), 5.05 (s, 2 H), 6.94 (d, J = 8.6 Hz, 2 H), 7.15 (d, J = 8.6 Hz, 2 H), 7.28–7.47 (m, 5 H). Guaymasol (+)-1: Yield: 78% (55 mg from 100 mg of 13a); colourless oil; [α]_D +23.5 (c = 0.4, CHCl₃) {see ref. 4: [α]_D +30.4 (c = 1.1, CHCl₃)}. ¹H NMR (400 MHz, CDCl₃): δ = 0.92 (t, J = 6.9 Hz, 6 H), 1.20–1.37 (m, 1 H), 1.45–1.59 (m, 1 H), 1.74–1.91 (m, 1 H), 1.93 (s, 2 H), 2.66 (dd, J = 13.9, 8.5 Hz, 1 H), 2.83 (dd, J = 13.9, 3.9 Hz, 1 H), 3.52–3.64 (m, 2 H), 6.77 (d, J = 8.5 Hz, 2 H), 7.09 (d, J = 8.5 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 22.0, 23.8, 24.7, 39.4, 42.9, 71.8, 75.6, 115.7, 130.0, 130.7, 154.5. HRMS (ESI): m/z [M + Na] calcd for C₁₃H₂₀NaO₃: 247.1305; found: 247.1297.

Supplementary Material

Supporting Information