Regioselective Oxidative Coupling Approach to the Synthesis of (±)-Matairesinol and (±)-Secoisolariciresinol

Fuqiang Zhu; Wenling Li; Qian Wang; Zijie Hou

doi:10.1055/s-2006-947317

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Synlett 2006(11): 1780-1782
DOI: 10.1055/s-2006-947317

LETTER

Regioselective Oxidative Coupling Approach to the Synthesis of (±)-Matairesinol and (±)-Secoisolariciresinol

Fuqiang Zhu, Wenling Li, Qian Wang, Zijie Hou*
Department of Chemistry, State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China
Fax: +86(931)8912582; e-Mail: houzj@lzu.edu.cn;

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Publication History

Received 22 February 2006
Publication Date:
04 July 2006 (online)

Abstract
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Abstract

An efficient method for the synthesis of (±)-matairesinol and (±)-secoisolariciresinol is presented. By using 5-(tert-butyl)ferulic acid as a precursor, a regioselective oxidative coupling step was realized, which gave the desired coupling product in much higher yield (91%) than the literature value (ca. 20%).

Key words

(±)-matairesinol - (±)-secoisolariciresinol - synthesis - regioselective - oxidative coupling

References and Notes

1a Esterfield TH. Bee J. J. Chem. Soc. 1910, 97: 1028

Crossref Search in Google Scholar
1b Rahman MMA. Dewick PM. Jackson DE. Lucas JA. Phytochemistry 1990, 29: 1971

Crossref Search in Google Scholar
1c Agrawal PK. Rastogi RP. Phytochemistry 1982, 21: 1459

Crossref Search in Google Scholar
2a Rahman MA. Dewick PM. Mann S. Biol. Pharm. Bull. 2003, 26: 371

Crossref Search in Google Scholar
2b Chen JJ. Fang HY. Duh CY. Chen IS. Planta Med. 2005, 71: 470

Crossref Search in Google Scholar
2c Tiwari AK. Srinivas PV. Kumar SP. Rao IM. J. Agric. Food. Chem. 2001, 49: 4642

Crossref Search in Google Scholar
2d Schottner M. Spiteller G. J. Nat. Prod. 1998, 61: 119

Crossref Search in Google Scholar
2e Brown E. Daugan A. Heterocycles 1987, 26: 1169

Crossref Search in Google Scholar
2f Fischer J. Reynolds AJ. Sharp LA. Sherburn MS. Org. Lett. 2004, 6: 1345

Crossref Search in Google Scholar
2g Umezawa T. Davin LB. Yamamoto E. Kinston DG. Lewis NG. J. Chem. Soc., Chem. Commun. 1990, 1405

Crossref
3a Ward RS. Chem. Soc. Rev. 1982, 11: 75

Crossref Search in Google Scholar
3b Brown RCD. Swain NA. Synthesis 2004, 6: 811

Crossref Search in Google Scholar
3c Belletire JL. Fry DF. J. Org. Chem. 1987, 52: 2549

Crossref Search in Google Scholar
4 Takei Y. Mori K. Matsui M. Agric. Biol. Chem. 1973, 37: 637

Search in Google Scholar
5 Cartwright NJ. Haworth D. J. Chem. Soc. 1944, 535
6 Sarkanen KV. Wallis AFA. J. Chem. Soc., Perkin Trans. 1 1973, 1869

Crossref
7 Saleh SA. Tashtoush HI. Tetrahedron 1998, 54: 14157

Crossref Search in Google Scholar
9 Rosenwald HR. J. Am. Chem. Soc. 1952, 74: 4602

Crossref Search in Google Scholar
10 Coffield TH. Filbey AH. Ecke GG. Kolka AJ. J. Am. Chem. Soc. 1957, 79: 5019

Crossref Search in Google Scholar
14 Tashiro M. Yamato T. J. Org. Chem. 1979, 44: 3037

Crossref Search in Google Scholar
19 Ahmed R. Lehrer M. Stevenson R. Tetrahedron 1973, 29: 3753

Crossref Search in Google Scholar

8

5-(tert-Butyl)ferulic acid (6): white crystalline solid; mp 185-186 °C. IR (neat): 3506, 2957, 1681 cm^-1. ¹H NMR (300 MHz, acetone-d ₆): δ = 1.43 (s, 9 H, CH₃), 3.94 (s, 3 H, OCH₃), 6.38 (d, J = 15.9 Hz, 1 H, H-7), 7.15 (d, J = 1.8 Hz, 1 H, H-2), 7.27 (br s, 1 H, H-6), 7.62 (d, J = 15.9 Hz, 1 H, H-8). ¹³C NMR (75 MHz, acetone-d ₆): δ = 30.0, 35.1, 56.5, 108.3, 115.4, 122.0, 125.9, 136.0, 146.1, 148.0, 148.6, 168.5. MS (EI): m/z (%) = 250(8) [M⁺], 235 (100) [M - CH₃]⁺. HRMS (EI): m/z calcd for C₁₄H₁₈O₄ + H: 251.1278; found: 251.1281.

11

Compound 7: white solid; mp 218-220 °C. IR (neat): 3391, 2950, 1753, 1693, 1652, 1151 cm^-1. ¹H NMR (300 MHz, acetone-d ₆): δ = 1.40 (s, 18 H, CH₃), 3.88 (s, 6 H, OCH₃), 4.11 (d, J = 1.2 Hz, 2 H, H-1, -5), 5.79 (br s, 4 H, H-2, H-6), 6.96 (s, 2 H, H-2′, H-2′′), 6.97 (s, 2 H, H-6′, H-6′′). ¹³C NMR (75 MHz, acetone-d ₆): δ = 29.5 (CH₃), 35.0 (CMe₃), 48.9 (C-1, 5), 56.3 (OCH₃), 83.4 (C-2,6), 107.1 (C-2′, -2′′), 117.3 (C-6′, -6′′), 129.1 (C-1′, -1′′), 135.9 (C-5′, -5′′), 145.9 (C-4′, -4′′), 148.3 (C-3′, -3′′), 175.8 (C=O). MS (EI): m/z (%) = 498 (62) [M⁺], 483 (40) [M - CH₃]⁺, 57 (100). HRMS (EI): m/z calcd for C₂₈H₃₄O₈ + H: 499.2326; found: 499.2328.

12

Compound 8: white solid; mp 199-200 °C. IR (neat): 3525, 2955, 1701, 1593, 1297 cm^-1. ¹H NMR (300 MHz, acetone-d ₆): δ = 1.34 (s, 18 H, CH₃), 2.74-2.79 (m, 2 H, CH), 2.86-3.01 (m, 4 H, ArCH₂), 3.73 (s, 6 H, OCH₃), 6.68 (br s, 4 H, H-2, H-2′, H-6, H-6′). ¹³C NMR (75 MHz, acetone-d ₆): δ = 29.9, 35.1, 37.7, 50.8, 56.4, 110.8, 120.1, 130.4, 135.3, 143.6, 147.7, 178.3. EIMS: m/z (%) = 484 (10) [M - 18]⁺, 227 (10), 193 (100). HRMS (EI): m/z calcd for C₂₈H₃₈O₈ + Na: 525.2459; found: 525.2454.

13

Compound 9: pale yellow gum. IR (neat): 3524, 2955, 1767, 1595, 1232 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.36 (s, 9 H, CH₃), 1.39 (s, 9 H, CH₃), 2.40-2.70 (m, 4 H, H-7′, H-8, H-8′), 2.91 (dd, J = 14.0, 6.3 Hz, 1 H, H-7), 3.03 (dd, J = 14.0, 4.8 Hz, 1 H, H-7), 3.79 (s, 3 H, OCH₃), 3.82 (s, 3 H, OCH₃), 3.88 (dd, J = 9.3, 6.6 Hz, 1 H, H-9′,), 3.96 (dd, J = 9.0, 6.6 Hz, 1 H, H-9′), 5.89 (s, 1 H, OH), 5.91 (s, 1 H, OH), 6.33 (d, J = 1.2 Hz, 1 H, H-2′), 6.54 (d, J = 1.2 Hz, 1 H, H-2), 6.59 (d, J = 1.2 Hz, 1 H, H-6′), 6.69 (br s, 1 H, H-6). ¹³C NMR (75 MHz, CDCl₃): δ = 29.6, 29.7, 34.8, 35.2, 38.9, 41.3, 47.1, 56.3, 71.6, 108.7, 109.5, 119.3, 120.1, 128.1, 128.3, 135.5, 135.8, 143.1, 143.2, 146.8, 147.0, 179.2. MS (EI): m/z (%) = 470 (8) [M⁺], 193 (100). HRMS (EI): m/z calcd for C₂₈H₃₈O₆ + NH₄: 488.3007; found: 488.3009.

15

Compound 10: colorless oil. IR(neat): 3526, 2956, 1730, 1595, 1372 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.18 (t, J = 6.9 Hz, 6 H, CH₂CH₃), 1.36 (s, 18 H, CH₃), 2.86-2.89 (m, 2 H, CH), 2.90-2.96 (m, 4 H, ArCH₂), 3.77 (s, 6 H, OCH₃), 4.08 (q, J = 6.9 Hz, 4 H, CH₂CH₃), 5.87 (s, 2 H, OH), 6.43 (s, 2 H, H-2, H-2′), 6.65 (s, 2 H, H-6, H-6′). ¹³C NMR (75 MHz, CDCl₃): δ = 14.1, 29.3, 34.5, 35.7, 48.1, 55.9, 60.5, 108.8, 119.7, 128.2, 134.6, 142.6, 146.4, 173.7. MS (EI): m/z (%) = 558 (14) [M⁺], 279 (10), 193 (88), 149 (100). HRMS (EI): m/z calcd for C₃₂H₄₆O₈ + H: 559.3265; found: 559.3267.

16

Compound 11: colorless oil. IR (neat): 3429, 2934, 1727, 1516 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.21 (t, J = 7.2 Hz, 6 H, CH₂CH₃), 2.83-2.86 (m, 2 H CH), 2.91-2.96 (m, 4 H, ArCH₂), 3.78 (s, 6 H, OCH₃), 4.10 (q, J = 7.2 Hz, 4 H, CH₂CH₃), 5.49 (s, 2 H, OH), 6.48 (s, 2 H, H-2, H-2′), 6.59 (d, J = 8.1 Hz, 2 H, H-6, H-6′), 6.79 (d, J = 8.1 Hz, 2 H, H-5, H-5′). ¹³C NMR (75 MHz, CDCl₃): δ = 14.1, 35.3, 47.5, 55.6, 60.6, 112.2, 114.0, 121.9, 130.5, 144.1, 146.3, 179.5. MS (EI): m/z (%) = 446 (10) [M⁺], 277 (31), 223 (24), 177 (28), 149 (53), 137 (100). HRMS (EI): m/z calcd for C₂₄H₃₀O₈ + H: 447.2013; found: 447.2021.

17

(±)-Matairesinol (1): pale yellow solid; mp 66-67 °C. IR (neat): 3418, 2935, 1760, 1606, 1239 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 2.40-2.63 (m, 4 H, H-7, H-8, H-8′), 2.87 (dd, J = 14.2, 6.8 Hz, 1 H, H-7′), 2.95 (dd, J = 14.2, 5.2 Hz, 1 H, H-7′), 3.80 (s, 6 H, OCH₃), 3.89 (dd, J = 9.2, 7.2 Hz, 1 H, H-9), 4.15 (dd, J = 8.8, 7.2 Hz, 1 H, H-9), 5.64 (br s, 2 H, OH), 6.40 (d, J = 1.6 Hz,1 H, H-2), 6.50 (dd, J = 8.0, 2.0 Hz, 1 H, H-6), 6.59 (dd, J = 8.0, 2.0 Hz, 1 H, H-6′), 6.60 (br s, 1 H, H-2′), 6.79 (d, J = 8.4 Hz,1 H, H-5), 6.81 (d, J = 8.4Hz, 1 H, H-5′). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 33.7, 36.9, 40.9, 45.7, 55.4, 55.5, 70.8, 112.6, 113.4, 115.4, 120.7, 120.6, 128.9, 129.7, 144.9, 145.1, 147.4, 147.5, 178.6. MS (EI): m/z (%) = 358 (4) [M⁺], 137 (100). HRMS (EI): m/z calcd for C₂₀H₂₂O₆ + NH₄: 376.1755; found: 376.1754.

18

(±)-Secoisolariciresinol (2): white solid; mp 116-117 °C. IR (neat): 3351, 2933, 1515 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.85 (br s, 2 H, H-8, H-8′), 2.64 (dd, J = 13.5, 6.9 Hz, 2 H, H-7, H-7′), 2.74 (dd, J = 13.5, 8.1 Hz, 2 H, H-7, H-7′), 3.54 (dd, J = 12, 4.2 Hz, 2 H, H-9, H-9′), 3.78-3.85 (m, 2 H, H-9, H-9′), 3.81 (s, 6 H, OCH₃), 6.58 (s, 2 H, H-2, H-2′), 6.62 (d, J = 8.4 Hz, 2 H, H-6, H-6′), 6.80 (d, J = 8.4 Hz, 2 H, H-5, H-5′). ¹³C NMR (75 MHz, CDCl₃): δ = 35.9, 43.8, 55.8, 60.8, 111.4, 114.1, 121.7, 132.4, 143.8, 146.4. MS (EI): m/z (%) = 362 (11) [M⁺], 277 (6), 189 (6), 137 (100). HRMS (EI): m/z calcd for C₂₀H₂₆O₆ + NH₄: 380.2068; found: 380.2061.