Synlett 2014; 25(20): 2883-2886
DOI: 10.1055/s-0034-1379480
letter
© Georg Thieme Verlag Stuttgart · New York

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
› Author Affiliations
Further Information

Publication History

Received: 17 July 2014

Accepted after revision: 25 September 2014

Publication Date:
17 October 2014 (online)


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.

Supporting Information

 
  • 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.