Unexpected Oxidation of ortho-Phenol Groups of Carnosol with m-Chloro-perbenzoic Acid

Joaquín G.  Marrero; Lucía  San Andrés Tejera; Javier G.  Luis; Matías L.  Rodríguez

doi:10.1055/s-2002-33513

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Synlett 2002(9): 1517-1519
DOI: 10.1055/s-2002-33513

LETTER

Unexpected Oxidation of ortho-Phenol Groups of Carnosol with m-Chloro-perbenzoic Acid

Joaquín G. Marrero, Lucía San Andrés Tejera*, Javier G. Luis, Matías L. Rodríguez
Instituto Universitario de Bio-Orgánica ‘Antonio González’, Universidad de La Laguna, Avenida Astrofísico Francisco Sánchez 2,38206 La Laguna, Tenerife, Canary Islands, Spain
Fax: +34(922)318571; e-Mail: landrest@ull.es;

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Publication History

Received 28 June 2002
Publication Date:
17 September 2002 (online)

Abstract
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Abstract

The oxidation reaction of carnosol (2) with m-chloroperbenzoic acid and sodium bicarbonate in dichloromethane gave an abietane diterpene (3) with an anhydride function on C ring. The conversion can be rationalized by a Baeyer-Villiger reaction from the initially generated ortho-quinone. The structure of this anhydride was confirmed by spectroscopic and X-ray crystallographic analysis. This reaction could be an important key step towards the synthesis of natural products such us drimane sesquiterpenes.

Key words

oxidation - natural products - abietatriene diterpenes - rearrangement - ring expansion

References

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11,12-Seco-11,12-epoxi-11,12-dioxo-8,13-abietadien-20,7β-olide(3): Mp: 226-228 °C; UV (EtOH): 207, 258 nm. IR (CHCl₃): 3440, 2962, 1744, 1725, 1290, 1112, 1046, 757 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 0.86 (3 H, s, Me-19), 0.90 (3 H, s, Me-18), 1.19 (3 H, d, J = 7.0 Hz, Me-16), 1.20 (3 H, d, J = 7.0 Hz, Me-17), 1.28 (1 H, dd, J ₁ = 3.2 Hz, J ₂ = 13.1 Hz, H-3), 1.60 (3 H, overlapping signal, H-2, H-3′, H-5), 1.87 (3 H, overlapping signal, H-1α, H-2′, H-6), 2.15 (1 H, m, H-6′), 2.68 (1 H, bd, J = 13.3 Hz, H-1β), 2.97 (1 H, hept, J = 7.0 Hz, H-15), 5.15 (1 H, dd, J ₁ = 1.5 Hz, J ₂ = 4.0 Hz, H-7), 6.37 (1 H, s, H-14). ¹³C NMR (75 MHz, CDCl₃): δ = 18.1 (t, C-2), 19.2 (q, C-18), 21.0 (q, C-16), 21.4 (q, C-17), 25.7 (t, C-6), 31.8 (q, C-19), 33.0 (d, C-15), 34.5 (s, C-4), 40.3 (t, C-3), 44.8 (d, C-5), 47.9 (s, C-10), 76.6 (d, C-7), 124.0 (d, C-14), 134.6 (s, C-9), 144.6 (s, C-8), 147.4 (s, C-13), 155.6 (s, C-11), 160.7 (s, C-12), 172.7 (s, C-20). MS-FAB: m/z (%) = 345 (14) [M⁺], 317 (6), 299 (20), 289 (11), 139 (13), 133 (41), 89 (24), 77 (11). HRMS-FAB: m/z = 345.1690 (calcd for C₂₀H₂₅O₅: 345.1702).

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A. L. Spek, PLATON. A multipurpose crystallographic tool, Utrecht University, Utrecht, Netherlands(2001). Crystallographic Data for (3): Colourless irregular shaped crystals, C₂₀H₄₈O₅, M_w = 344.4, monoclinic system, space group P2₁, Z = 2, a = 6.530(2) Å, b = 11.034(3) Å, c = 12.705(3) Å, β = 103.76(2)º, V = 889.1(4) Å³, D_c = 1.29 gcm^-3, F(000) = 368, µ (MoKα) = 0.09 mm^-1. The intensity data of all unique reflections within the θ range 2.5-26.3º were collected at r.t. on an Enraf-Nonius CAD4 diffractometer, using MoKα radiation and graphite monochromador. Three standard reflections monitored every 2 h of X-ray exposure showed no significant decay of the intensity. A total of 1260 unique reflections were recorded of which 592 were considered as observed under F₀>4σ (F₀). The intensities were corrected for Lorentz and polarization factors, but no absorption correction was made. The structure was solved by direct methods using SHELXS86, refinement was performed with SHELXL93, using full-matrix least squares with anisotropic thermal parameters for all the non-H atoms. The H-atoms were placed in idealized positions and added in the last steps of the refinement as a fixed isotropic contribution. The refinement converged at R1 = 6.06% and wR2 = 18.23%, with a goodness of fit for F [2] of 1.01, the largest peak on the final difference map was 0.22 e/Å [3] . Crystallographic data of(3), including atomic coordinates, have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication nº CCDC 188402. Copies of the data can be obtained free of charge on applications to the Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, U.K. (Fax: +44(1223)336033, e-mail: deposit@ccdc.cam.ac.uk).

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11,12-Seco-8,13-abietadien-20,7β-lacton-11,12-dioic Acid Dimethyl Ester (4): UV (EtOH): 246 nm. IR (CHCl₃): 2924, 1754, 1722, 1242, 1091, 1031 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 0.83 (3 H, s, Me-19), 0.88 (3 H, s, Me-18), 1.08 (3 H, d, J = 7.0 Hz, Me-16), 1.09 (3 H, d, J = 7.0 Hz, Me-17), 2.47 (1 H, bd, J = 14.2 Hz, H-1β), 2.74 (1 H, hept, J = 6.8 Hz, H-15), 3.75 (3 H, s, -OCH₃), 3.77 (3 H, s,
-OCH₃), 5.00 (1 H, s, H-7), 6.22 (1 H, s, H-14). ¹³C NMR (75 MHz, CDCl₃): δ = 18.3 (t, C-2), 19.2 (q, C-18), 21.4 (q, C-16), 21.5 (q, C-17), 26.9 (t, C-1), 28.0 (t, C-6), 31.8 (q, C-19), 32.6 (d, C-15), 34.2 (s, C-4), 40.5 (t, C-3), 45.4 (d, C-5), 47.2 (s, C-10), 52.0 (t, 2 × -OCH₃), 75.9 (d, C-7), 123.8 (d, C-14), 136.8 (s, C-9), 142.0 (s, C-8), 144.0 (s, C-13), 165.1 (s, C-11), 168.8 (s, C-12), 174.2 (s, C-20). MS (EI): m/z (%) = 390 (11) [M⁺], 347 (24), 331 (100), 299 (29), 255 (44), 211 (10), 69 (15). HRMS (EI): m/z = 390.2041 (calcd for C₂₂H₃₀O₆: 390.2042).

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11,12- O -Didehydrocarnosol (5): UV (EtOH): 207 nm. IR (CHCl₃): 2960, 1750, 1665, 1462, 1109, 1029, 755 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 0.87 (3 H, s, Me-19), 0.89 (3 H, s, Me-18), 1.12 (6 H, d, J = 7.0 Hz, Me-16, Me-17), 1.23 (1 H, m, H-3), 1.53 (1 H, bd, J = 13.3 Hz, H-3′), 1.65 (2 H, overlapping signal, H-2, H-5), 1.87 (1 H, dt, H-2′), 1.97 (1 H, m, H-6), 2.20 (1 H, m, H-6′), 2.30 (1 H, td, J ₁ = 4.6 Hz, J ₂ = 14.0 Hz, H-1α), 2.68 (1 H, bd, J = 14.4 Hz, H-1β), 2.97 (1 H, hept, J = 7.0 Hz, H-15), 5.19, 5.20 (1 H, dd, J ₁ = 1.4 Hz, J ₂ = 4.0 Hz, H-7), 6.67 (1 H, s, H-14). ¹³C NMR (75 MHz, CDCl₃): δ = 18.2 (t, C-2), 19.3 (q, C-18), 21.3 (q, C-16), 21.3 (q, C-17), 27.0 (t, C-1), 27.8 (t, C-6), 27.8 (d, C-15), 32.0 (q, C-19), 34.4 (s, C-4) 40.5 (t, C-3), 44.8 (d, C-5), 48.7 (s, C-10), 76.4 (d, C-7), 129.6 (d, C-14), 135.6 (s, C-9), 151.1 (s, C-13), 173.3 (s, C-20), 176.2 (s, C-11), 179.2 (s, C-12). MS (EI): m/z (%) = 328 (5) [M⁺], 284 (43), 215 (100), 204 (17), 165 (14), 141 (14), 55(20). HRMS (EI): m/z = 328.1696 (calcd for C₂₀H₂₄O₄: 328.1675).