Synthesis of Hemitectol, Tectol, and Tecomaquinone I

Melissa M. Cadelis; David Barker; Brent R. Copp

doi:10.1055/s-0032-1317541

RSS-Feed abonnieren

Bitte kopieren Sie die angezeigte URL und fügen sie dann in Ihren RSS-Reader ein.

https://www.thieme-connect.de/rss/thieme/de/10.1055-s-00000083.xml

Teilen / Bookmarken

Facebook X Linkedin Weibo

PDF herunterladen

Synlett 2012; 23(20): 2939-2942
DOI: 10.1055/s-0032-1317541

letter

Synthesis of Hemitectol, Tectol, and Tecomaquinone I

Melissa M. Cadelis

School of Chemical Sciences, The University of Auckland, Private Bag 92019, Auckland 1142, New Zealand Fax: +64(9)3737422 eMail: b.copp@auckland.ac.nz

,

David Barker

School of Chemical Sciences, The University of Auckland, Private Bag 92019, Auckland 1142, New Zealand Fax: +64(9)3737422 eMail: b.copp@auckland.ac.nz

,

Brent R. Copp*

School of Chemical Sciences, The University of Auckland, Private Bag 92019, Auckland 1142, New Zealand Fax: +64(9)3737422 eMail: b.copp@auckland.ac.nz

› Institutsangaben

Weitere Informationen

Publikationsverlauf

Received: 06. September 2012

Accepted after revision: 17. Oktober 2012

Publikationsdatum:
13. November 2012 (online)

Abstract
Volltext
Referenzen

Artikel einzeln kaufen Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

The first total syntheses of Tectona grandis (teak) natural products hemitectol and tectol are described. The observation of spontaneous dimerisation of hemitectol to tectol suggests the monomer is the true natural product and that the dimer is an artifact of isolation.

Key words

cyclisation - dimerisation - quinone - ring closure - total synthesis

References and Notes
1 Chan ST. S, Pearce AN, Januario AH, Page MJ, Kaiser M, McLaughlin RJ, Harper JL, Webb VL, Barker D, Copp BR. J. Org. Chem. 2011; 76: 9151

Crossref Suche in Google Scholar
2 Sumthong P, Romero-González RR, Verpoorte R. J. Wood. Chem. Tech. 2008; 28: 247

Crossref Suche in Google Scholar
3 Sandermann W, Simatupang MH. Chem. Ber. 1964; 97: 588

Crossref Suche in Google Scholar
4 Lemos TL. G, Monte FJ. Q, Santos AK. L, Fonseca AM, Santos HS, Oliveira MF, Costa SM. O, Pessoa OD. L, Braz-Filho R. Nat. Prod. Res. 2007; 21: 529

Crossref Suche in Google Scholar
5 tert-Butyl(4-methoxynaphthalen-1-yloxy)dimethylsilane (8) IR (ATR): 2929, 2857, 1625, 1596, 1461, 1384, 1273, 1095 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 8.25–8.23 (m, 2 H, H-5, H-8), 7.60–7.56 (m, 2 H, H-6, H-7), 6.86 (d, J = 8.5 Hz, 1 H, H-3), 6.73 (d, J = 8.5 Hz, 1 H, H-2), 4.03 (s, 3 H, OCH₃), 1.20 (s, 9 H, H-4′, H-5′, H-6′), 0.36 (s, 6 H, H-1′, H-2′). ¹³C NMR (100 MHz, CDCl₃): δ = 149.9 (C-1), 145.2 (C-4), 128.6 (ArC), 126.6 (ArC), 125.8 (ArCH), 125.5 (ArCH), 122.5 (ArCH), 122.0 (ArCH), 111.9 (C-3), 103.5 (C-2), 55.7 (OCH₃), 26.0 (C-4′, C-5′, C-6′), 18.5 (C-3′), –4.2 (C-1′, C-2′). ESI-HRMS: m/z calcd for C₁₇H₂₅O₂Si [MH⁺]: 289.1618; found: 289.1624.
6 4-(tert-Butyldimethylsiloxy)naphthalene-1-ol (9) IR (ATR): 3255, 2929, 1595, 1471, 1347, 1266, 1069 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 8.10–8.09 (m, 2 H, H-5, H-8), 7.50–7.47 (m, 2 H, H-6, H-7), 6.68 (s, 2 H, H-2, H-3), 1.09 (s, 9 H, H-4′, H-5′, H-6′), 0.24 (s, 6 H, H-1′, H-2′). ¹³C NMR (100 MHz, CDCl₃): δ = 145.4 (C-1), 138.7 (C-4), 126.4 (2 × Ar-C), 125.7 (ArCH), 125.5 (ArCH), 122.7 (ArCH), 121.5 (ArCH), 112.0 (C-2), 108.3 (C-3), 25.9 (C-4′, C-5′, C-6′), 18.4 (C-3′), –4.3 (C-1′, C-2′). ESI-HRMS: m/z calcd for C₁₆H₂₃O₂Si [MH⁺]: 275.1462; found: 275.1462.
7 Lee YR, Kim YM. Helv. Chim. Acta 2007; 90: 2401

Crossref Suche in Google Scholar
8 tert-Butyl(2,2-dimethyl-2H-benzo[h]chromen-6-yloxy)dimethylsilane (10) IR (ATR): 2930, 1595, 1457, 1409, 1370, 1274, 1084 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 8.15–8.03 (m, 2 H, H-7, H-10), 7.43–7.40 (m, 2 H, H-8, H-9), 6.54 (s, 1 H, H-5), 6.35 (d, J = 9.7 Hz, 1 H, H-4), 5.63 (d, J = 9.7 Hz, 1 H, H-3), 1.49 (s, 6 H, H-11, H-12), 1.08 (s, 9 H, H-4′, H-5′, H-6′), 0.24 (s, 6 H, H-1′, H-2′). ¹³C NMR (100 MHz, CDCl₃): δ = 144.8 (C-6), 142.4 (C-10b), 129.9 (C-3), 128.3 (ArC), 126.0 (ArC), 125.5 (ArCH), 125.3 (ArCH), 122.9 (C-4), 122.5 (ArCH), 121.8 (ArCH), 115.0 (C-4a), 110.9 (C-5), 76.2 (C-2), 27.6 (C-11, C-12), 25.9 (C-4′, C-5′, C-6′), 18.4 (C-3′), –4.2 (C-1′, C-2′). ESI-HRMS: m/z calcd for C₂₁H₂₉O₂Si [MH⁺]: 341.1931; found: 341.1919.
9 Hemitectol (6) Dark yellow oil. IR (ATR): 3419, 2973, 1586, 1451, 1402, 1369, 1360, 1257, 1070 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 8.03–7.96 (m, 2 H, H-7, H-10), 7.46–7.37 (m, 2 H, H-8, H-9), 6.60 (s, 1 H, H-5), 6.43 (d, J = 9.5 Hz, 1 H, H-4), 5.75 (d, J = 9.5 Hz, 1 H, H-3), 1.42 (s, 6 H, H-11, H-12). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 146.4 (C-6), 143.7 (C-10b), 130.4 (C-3), 125.6 (ArCH), 125.1 (ArC), 124.9 (ArC), 124.7 (ArCH), 122.6 (C-4), 122.1 (ArCH), 121.1 (ArCH), 115.2 (C-4a), 105.9 (C-5), 75.7 (C-2), 27.1 (C-11, C-12). ESI-HRMS: m/z calcd for C₁₅H₁₅O₂ [MH⁺]: 227.1067; found: 227.1063.
10 Tectol (5) White solid; 206–209 °C (lit.² 207–208 °C). IR (ATR): 3420, 2973, 1586, 1451, 1402, 1369, 1361, 1221, 1071 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 8.17–8.08 (m, 4 H, H-7, H-7′, H-10, H-10′), 7.52–7.44 (m, 4 H, H-8, H-8′, H-9, H-9′), 5.78 (d, J = 9.9 Hz, 2 H, H-4, H-4′), 5.59 (d, J = 9.9 Hz, 2 H, H-3, H-3′), 1.45 (s, 6 H, H-11, H-11′), 1.43 (s, 6 H, H-12, H-12′). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 144.1 (C-6, C-6′), 140.6 (C-10b, C-10b′), 130.0 (C-3, C-3′), 125.5 (2 × ArC), 125.4 (2 × ArCH), 125.1 (2 × ArC), 125.0 (2 × ArCH), 122.5 (2 × ArCH), 121.2 (2 × ArCH), 120.9 (C-4, C-4′), 115.9 (C-4a, C-4a′), 113.2 (C-5, C-5′), 75.2 (C-2, C-2′), 27.0 (C-11, C-11′, C-12, C-12′). ESI-HRMS: m/z calcd for C₃₀H₂₆O₄Na [MNa⁺]: 473.1723; found: 473.1714.
11 Bandaranayake WM, Crombie L, Whiting DA. J. Chem. Soc. 1971; 811
12 Tecomaquinone I (4) Green solid; mp 187–189 °C (lit.² 188–189 °C). IR (ATR): 3360, 2978, 1690, 1568, 1277, 1237, 1197, 1109 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 8.14–8.09 (m, 2 H, H-7, H-10), 8.07–8.05 (m, 1 H, H-2′), 8.04–8.01 (m, 1 H, H-5′), 7.95–7.86 (m, 2 H, H-3′, H-4′), 7.65–7.60 (m, 1 H, H-9), 7.57–7.53 (td, J = 7.0, 1.5 Hz, 1 H, H-8), 6.36 (d, J = 9.9 Hz, 1 H, H-4), 6.34 (d, J = 9.1 Hz, 1 H, H-7′), 5.62 (d, J = 9.9 Hz, 1 H, H-3), 5.44 (td, J = 9.0, 1.5 Hz, 1 H, H-8′), 2.03 (br s, 3 H, H-11′), 1.60 (s, 3 H, H-12), 1.59 (s, 3 H, H-10′), 1.55 (s, 3 H, H-11). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 182.8 (C-6′), 181.6 (C-1′), 146.5 (C-6), 142.4 (C-10b), 141.7 (C-9′), 135.9 (ArC), 135.4 (ArC), 134.0 (ArC), 133.8 (2 × ArCH), 132.9 (ArC), 131.3 (ArC), 128.2 (ArCH), 126.7 (ArCH), 126.5 (ArCH), 125.3 (ArCH), 125.3 (C-3), 124.7 (ArC), 123.8 (C-4), 122.5 (ArCH), 121.8 (ArCH), 117.6 (C-8′), 113.0 (C-4a), 111.2 (C-5), 75.5 (C-2), 67.3 (C-7′), 28.2 (C-12), 25.5 (C-10′), 25.2 (C-11), 18.7 (C-11′). ESI-HRMS: m/z calcd for C₃₀H₂₅O₄ [MH⁺]: 449.1747; found: 449.1726.
13 Gonzalez AG, Barroso JT, Cardona RJ, Medina JM, Luis FR. An. Quim. 1977; 73: 538

Suche in Google Scholar
14 Tohma H, Morioka H, Takizawa S, Arisawa M, Kita Y. Tetrahedron 2001; 57: 345

Crossref Suche in Google Scholar
15 Furan Dimer A (13) Brown solid; mp 112.1–115.1 °C. IR (ATR): 2938, 1637, 1598, 1457, 1382, 1100 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 8.18–8.17 (m, 4 H, H-8, H-8′, H-9, H-9′), 7.52–7.46 (m, 4 H, H-7, H-10, H-7′, H-10′), 6.77 (s, 2 H, H-5, H-5′), 4.94 (d, J = 6.5 Hz, 2 H, H-4, H-4′), 3.97 (s, 6 H, OCH₃, OCH₃′), 2.63 (d, J = 6.5 Hz, 2 H, H-3, H-3′), 1.57 (s, 6 H, H-11, H-11′), 1.46 (s, 6 H, H-12, H-12′). ¹³C NMR (100 MHz, CDCl₃): δ = 149.7 (C-6, C-6′), 142.8 (C-10b, C-10b′), 126.3 (2 × ArC), 126.3 (2 × ArC), 126.0 (2 × ArCH), 126.0 (2 × ArCH), 122.0 (2 × ArCH), 121.8 (2 × ArCH), 115.4 (C-4a, C-4a′), 77.3 (C-2, C-2′), 73.1 (C-4, C-4′), 55.8 (OCH₃, OCH₃′), 49.4 (C-3, C-3′), 27.9 (C-12, C-12′), 26.9 (C-11, C-11′). ESI-HRMS: m/z calcd for C₃₂H₃₃O₅ [MH⁺]: 497.2323; found: 497.2307.
16 Furan Dimer B (14) Brown solid; mp 216.0–218.6 °C. IR (ATR): 2938, 1637, 1598, 1457, 1382, 1100 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 8.23–8.15 (m, 4 H, H-7, H-7′, H-10, H-10′), 7.52–7.42 (m, 4 H, H-8, H-8′, H-9, H-9′), 7.06 (s, 1 H, H-5), 6.96 (s, 1 H, H-5′), 5.13 (d, J = 8.3 Hz, 1 H, H-4), 4.88 (d, J = 10.5 Hz, 1 H, H-4′), 4.07 (s, 3 H, OCH₃), 4.01 (s, 3 H, OCH₃′), 2.74 (t, J = 8.3 Hz, 1 H, H-3), 2.10 (dd, J = 10.5, 8.3 Hz, 1 H, H-3′), 1.70 (s, 3 H, H-12′), 1.64 (s, 3 H, H-11), 1.60 (s, 3 H, H-11′), 1.17 (s, 3 H, H-12). ¹³C NMR (100 MHz, CDCl₃): δ = 150.0 (C-6′), 149.1 (C-6), 141.5 (C-10b), 141.0 (C-10b′), 126.6 (2 × ArCH), 126.1 (2 × ArCH), 125.9 (ArC), 125.9 (ArC), 125.5 (ArC), 125.1 (ArC), 122.0 (ArCH), 121.9 (2 × ArCH), 121.6 (ArCH), 119.8 (C-4a′), 116.6 (C-4a), 102.8 (C-5), 99.4 (C-5′), 80.6 (C-2′), 77.8 (C-4), 76.6 (C-2′), 76.2 (C-4′), 56.0 (OCH₃), 55.8 (OCH₃′), 55.6 (C-3′), 49.6 (C-3), 31.7 (C-12′), 29.9 (C-11), 24.0 (C-11′), 22.6 (C-12). ESI-HRMS: m/z calcd for C₃₂H₃₃O₅ [MH⁺]: 497.2323; found: 497.2305.
17 Fraga BM, Garcia VP, Gonzalez AG, Hernandez MG, Hanson JR, Hitchcock PB. J. Chem. Soc. 1983; 2687

RSS-Feed abonnieren

Teilen / Bookmarken

Synthesis of Hemitectol, Tectol, and Tecomaquinone I

Publikationsverlauf

Abstract

Key words

References and Notes