Vanadium(V)-Catalyzed Oxidation of (3R)-Linalool - The Selective Formation of Furanoid Linalool Oxides and their Conversion into Isocyclocapitelline Derivatives

Jens  Hartung; Simone  Drees; Barbara  Geiss; Philipp  Schmidt

doi:10.1055/s-2003-36793

LETTER

Vanadium(V)-Catalyzed Oxidation of (3R)-Linalool - The Selective Formation of Furanoid Linalool Oxides and their Conversion into Isocyclocapitelline Derivatives

Jens Hartung*, Simone Drees, Barbara Geiss, Philipp Schmidt
Institut für Organische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg
Fax: +49(931)8884606; e-Mail: hartung@chemie.uni-wuerzburg.de;

Abstract

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Abstract

Oxidation of (3R)-linalool (2) with tert-butyl hydroperoxide (TBHP) occurs at the 6,7-position to selectively afford linalool oxide cis-1, if catalyzed by vanadium(V) Schiff base complexes 4. Substituted tetrahydrofuran cis-1 and its isomer trans-1 served as starting materials for short concise syntheses of β-carbolines cis-3 and trans-3 which are lower homologues of alkaloids (-)-isocyclocapitelline and (+)-cyclocapitelline.

Key words

tert-butyl hydroperoxide - linalool oxide - oxidation - Schiff base complex - vanadium

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References

<A NAME="RG29902ST-1">1</A> Phuong NM. Sung TV. Porzel A. Schmidt J. Merzweiler K. Adam G. Phytochemistry 1999, 52: 1725

<A NAME="RG29902ST-2">2</A> Peng J.-N. Feng X.-Z. Zheng Q.-T. Liang X.-T. Phytochemistry 1997, 46: 1119

<A NAME="RG29902ST-3A">3a</A> Wüst M. Monsandl A. Eur. Food Res. Technol. 1999, 209: 3

<A NAME="RG29902ST-3B">3b</A> Winterhalter P. Katzenberger D. Schreier P. Phytochemistry 1986, 25: 1347

<A NAME="RG29902ST-4A">4a</A> Zhang JX. Wang G.-X. Xie P. Chen S.-F. Liang XT. Tetrahedron Lett. 2000, 41: 2211

<A NAME="RG29902ST-4B">4b</A> Wang GX. Zhang JX. Chen SF. Liang XT. Chin. Chem. Lett. 2001, 12: 199

<A NAME="RG29902ST-4C">4c</A> Mahboobi S. Koller M. Schollmeyer D. Monatsh. Chem. 2000, 131: 383

<A NAME="RG29902ST-5A">5a</A> Klein E. Farnow H. Rojahn W. Liebigs Ann. Chem. 1964, 675: 73

<A NAME="RG29902ST-5B">5b</A> Prileschajew N. Ber. Dtsch.Chem. Ges. 1909, 42: 4811

<A NAME="RG29902ST-6">6</A> Villa de . De Vos DE. Montes de CC. Jacobs A. Tetrahedron Lett. 1998, 39: 8521

<A NAME="RG29902ST-7A">7a</A> Sams CK. Jørgensen KA. Acta Chim. Scand. 1995, 49: 839

<A NAME="RG29902ST-7B">7b</A> Sheldon RA. In The Chemistry of Functional Groups, Peroxides Patai S. Wiley; Chichester: 1983. p.161-199

<A NAME="RG29902ST-7C">7c</A> Sharpless KB. Verhoeven TR. Aldrichimica Acta 1979, 12: 63

<A NAME="RG29902ST-8A">8a</A> Ohloff G. Giersch W. Schulte-Elte KH. Enggist P. Demole E. Helv. Chim. Acta 1980, 63: 1582

<A NAME="RG29902ST-8B">8b</A> Sharpless KB. Michaelson RC. J. Am. Chem. Soc. 1973, 6136

<A NAME="RG29902ST-9">9</A> Sheldon RA. In Aspects of Homogeneous Catalysis Vol. 4: Ugo E. Reidel Publishing; Dordrecht: 1981. p.3-70

<A NAME="RG29902ST-10A">10a</A> González IC. Forsyth CJ. J. Am. Chem. Soc. 2000, 122: 9099

<A NAME="RG29902ST-10B">10b</A> Hashimoto M. Kan T. Nozaki K. Yanagiya M. Shirahama H. Matsumoto T. J. Org. Chem. 1990, 55: 5088

<A NAME="RG29902ST-10C">10c</A> Corey EJ. Ha D.-C. Tetrahedron Lett. 1988, 29: 3171

<A NAME="RG29902ST-11">11</A> Hartung J. Greb M. J. Organometal. Chem. 2002, 661: 67

<A NAME="RG29902ST-12">12</A> Mimoun H. Mignard M. Brechot P. Saussine L. J. Am. Chem. Soc. 1986, 108: 3711

<A NAME="RG29902ST-13">13</A> Hartung J. Schmidt P. Synlett 2000, 367

Hartung, J.; Drees, S.; Greb, M.; Schmidt, P.; Svoboda, I.; Fuess, H.; Murso, A.; Stalke, D. Eur. J. Org. Chem., submitted.

<A NAME="RG29902ST-15">15</A> Weinert B. Wüst M. Mosandl A. Hanssum H. Phytochem. Anal. 1998, 9: 10

A solution of (3R)-linalool (2) (154 mg, 1.00 mmol) in CHCl₃ (5 mL) and vanadium(V) complex 4b (36.3 mg, 0.10 mmol) was stirred for 5 min at 25 °C. Subsequently, TBHP (273 µL, 5.5 M in nonane, 1.50 mmol) was added and the deep red reaction mixture was stirred for additional 12 h at 25 °C. Afterwards, the solvent was removed at 250 mbar/40 °C to afford a dark brown residue which was filtered through a short pad of Al₂O₃ in order to remove the catalyst. The product was washed with Et₂O (75 mL) from the column. Combined filtrate and eluate were concentrated in vacuo to provide an oil which was distilled under reduced pressure. The distillate was purified by column chromatography [SiO₂, petroleum ether-Et₂O-acetone, 5:2:1 (v/v/v); R_f cis-1 = 0.48; R_f trans-1 = 0.45] to provide 111 mg (65%) linalool oxide 1: colourless liquid, bp 80 °C/10 mbar (Kugelrohr, Lit. 78 °C/13 Torr), cis:trans = 61:39. cis-1: [α]_D ²⁵ +29.1 (c 1.1, CHCl₃), ref. [17] : [α]_D ²⁵ +11.7 (c = 0.1, CH₃OH). ¹H NMR (250 MHz, CDCl₃): δ = 1.11 (s, 3 H), 1.20 (s, 3 H), 1.29 (s, 3 H), 1.75-1.89 (m, 4 H), 2.05 (s br, 1 H, OH), 3.84 (dd, J = 8, 7 Hz, 1 H), 4.97 (dd, J = 11, 2 Hz, 1 H), 5.17 (dd, J = 17, 2 Hz, 1 H), 5.96 (dd, J = 17, 11 Hz, 1 H). trans-1: [α]_D ²⁵ -13.1 ( c 1.0, CHCl₃), ref. [17] : [α]_D ²⁵ -10.1 (c 0.1, CH₃OH). ¹H NMR (250 MHz, CDCl₃): δ = 1.10 (s, 3 H), 1.21 (s, 3 H), 1.29 (s, 3 H), 1.66-1.74 (m_c, 1 H), 1.75-1.93 (m, 3 H), 2.05 (s, br., 1 H, OH), 3.78 (t, J = 7 Hz, 1 H), 4.98 (dd, J = 11, 2 Hz, 1 H), 5.18 (dd, J = 17, 2 Hz, 1 H), 5.85 (dd, J = 17, 11 Hz, 1 H).

<A NAME="RG29902ST-17A">17a</A> Castrette M. Axiotis GP. J. Organometal. Chem. 1981, 206: 139

<A NAME="RG29902ST-17B">17b</A> David L. Veschambre H. Tetrahedron Lett. 1984, 25: 543

Control experiments [14] indicated that vanadium(V) complex 4b catalyzes oxidation of racemic mixtures of chiral bishomoallylic alcohols without kinetic resolution.

Tungsten-catalyzed oxidations:

<A NAME="RG29902ST-19A">19a</A> Sakaguchi S. Nishiyama Y. Ishii Y. J. Org. Chem. 1996, 61: 5307

<A NAME="RG29902ST-19B">19b</A> Villa de OAL. Sels BF. De Vos DE. Jacobs PA. J. Org. Chem. 1999, 64: 7267

<A NAME="RG29902ST-20">20</A> Lempers HEB. Ripollès i Garcia A. Sheldon RA. J. Org. Chem. 1998, 63: 1408

Titanium and titanium silicate-catalyzed oxidations:

<A NAME="RG29902ST-21A">21a</A> Schofield LJ. Kerton WJ. McMorn P. Bethell D. Ellwood S. Hutchings GJ. J. Chem. Soc., Perkin Trans. 2 2002, 1475

<A NAME="RG29902ST-21B">21b</A> Lattanzi A. Della Sala G. Russo M. Scettri A. Synlett 2001, 1479

<A NAME="RG29902ST-21C">21c</A> Corma A. Iglesias M. Sánchez F. J. Chem. Soc., Chemm. Commun. 1995, 1635

<A NAME="RG29902ST-22">22</A> Felix D. Malera A. Seibl J. Kováts E. Helv. Chim. Acta 1963, 46: 1513

<A NAME="RG29902ST-23">23</A> Yang D. Zhang C. J. Org. Chem. 2001, 66: 4814

cis-1-[5-(1-Hydroxy-1-methylethyl)-2-methyltetrahydro-furan-2-yl]-1,2,3,4-tetrahydro-9H-β-carboline: colorless crystals, mp 119 °C; [α]_D ²⁵ -22.9 (c 0.82, CHCl₃). ¹H NMR (250 MHz, CDCl₃): δ = 1.08 (s, 3 H), 1.24 (s, 3 H), 1.38 (s, 3 H), 1.80-2.16 (m, 4 H), 2.78 (ddd, J = 12.1, 7.9, 5.5 Hz, 2 H), 3.21 (ddd, J = 12.5, 9.8, 5.5 Hz, 2 H), 4.02 (t, J = 7.0 Hz, 1 H), 4.06 (s, 1 H), 7.00-7.19 (m, 2 H), 7.24-7.36 (m, 1 H), 7.49 (m_c, J = 7.0 Hz, 1 H), 8.75 (s, 1 H), 10.23 (s, 1 H). ¹³C NMR (63 MHz, CDCl₃): δ = 20.5, 22.6, 25.0, 25.8, 27.4, 36.0, 43.9, 61.2, 71.2, 83.0, 85.6, 110.9, 112.8, 118.0, 119.0, 121.4, 135.4, 156.7, 175.5. MS (EI, 70 eV,): m/z (%) = 314 (3) [M⁺], 171 (100) [C₁₁H₁₁N₂ ⁺], 143 (6) [C₈H₁₅O₂ ⁺], 84 (11) [C₅H₈O⁺], 43 (10) [C₃H₆ ⁺]. UV/Vis (EtOH): λ_max (lg ε): 232 nm (3.76), 282 (3.81), 373 (2.46). C₁₉H₂₆N₂O₂ (314.4): Calcd C, 72.58; H, 8.33; N, 8.91. Found: C, 67.25; H, 8.26; N, 7.99. trans-1-[5-(1-Hydroxy-1-methylethyl)-2-methyltetrahydrofuran-2-yl]-1,2,3,4-tetrahydro-9H-β-carboline: colorless solid, mp 113 °C. [α]_D ²⁵ -19.5 (c 0.63, CHCl₃). ¹H NMR (250 MHz, CDCl₃): δ = 1.08 (s, 3 H), 1.22 (s, 3 H), 1.40 (s, 3 H), 1.89-2.22 (m, 4 H), 2.68-2.90 (m, 2 H), 3.22 (ddd, J = 15.0, 9.8, 5.2 Hz, 2 H), 3.99 (dd, J = 8.2, 5.4 Hz, 1 H), 4.08-4.12 (m, 1 H), 7.05-7.20 (m, 2 H), 7.33 (m_c, 1 H), 7.50 (m_c, 1 H), 8.60 (s, 1 H). ¹³C NMR (63 MHz, CDCl₃): δ = 21.6, 22.6, 24.6, 26.1, 28.8, 36.8, 43.0, 60.6, 70.4, 77.0, 86.6, 110.1, 110.9, 118.0, 119.0, 121.5, 142.3, 153.4, 174.1. MS (EI, 70 eV): m/z (%) = 314(3) [M⁺], 171(100) [C₁₁H₁₁N₂ ⁺], 143(6) [C₈H₁₅O₂ ⁺], 84(11) [C₅H₈O⁺], 43(10) [C₃H₆ ⁺]. UV/Vis (EtOH): λ_max (lg ε): 242 nm (4.52), 282 (3.85), 371 (2.57). C₁₉H₂₂N₂O₂ (314.4): Calcd C, 72.58; H, 8.33; N, 8.91. Found: C, 67.94; H, 8.06; N, 7.78.

cis-1-[5-(1-Hydroxy-1-methylethyl)-2-methyltetrahydro-furan-2-yl]-9H-β-carboline cis-3: colorless solid, mp 161 °C. [α]_D ²⁵ -32.9 (c 0.57, CHCl₃). ¹H NMR (250 MHz, CDCl₃): δ = 1.23 (s, 3 H), 1.45 (s, 3 H), 1.78 (s, 3 H), 1.75-3.08 (m, 4 H), 4.15 (t, J = 7.3 Hz, 1 H), 7.24 (ddd, J = 7.8, 6.1, 1.8 Hz, 1 H), 7.52 (m_c, 2 H), 7.86 (d, J = 5.5 Hz, 1 H), 8.13 (d, J = 7.9 Hz, 1 H), 8.39 (d, J = 5.5 Hz, 1 H), 9.53 (s, 1 H). ¹³C NMR (63 MHz, CDCl₃): δ = 24.2, 26.2, 27.6, 27.9, 37.3, 73.3, 88.4, 90.2, 111.5, 113.4, 119.7, 121.6, 121.7, 128.3, 133.2, 136.1, 138.0, 143.2, 148.0. MS (EI, 70 eV):
m/z (%) = 310(17) [M⁺], 151(24) [C₁₆H₁₅N₂O⁺], 209 (100) [C₁₄H₁₂N₂ ⁺], 182 (11) [C₁₀H₁₆NO₂ ⁺], 43 (9) [C₂H₄O⁺]. UV/Vis (EtOH): λ_max (lg ε): 242 nm (4.52), 288 (4.26), 348 (3.77). C₁₉H₂₂N₂O₂ (310.4): Calcd C, 73.52; H, 7.14; N, 9.03. Found: C, 72.86; H, 7.11; N, 8.68. trans-1-[5-(1-Hydroxy-1-methylethyl)-2-methyltetrahydrofuran-2-yl]-9H-β-carboline trans-3: colorless solid, mp 158 °C. [α]_D ²⁵
-50.5 (c 0.5, CHCl₃). ¹H NMR (250 MHz, CDCl₃): δ = 1.25 (s, 3 H), 1.38 (s, 3 H), 1.72 (s, 3 H), 1.75-2.10 (m, 4 H), 4.15 (t, J = 7.6 Hz, 1 H), 7.22 (ddd, J = 7.9, 6.4, 1.5 Hz, 1 H), 7.48 (m_c, 2 H), 7.86 (d, J = 5.2 Hz, 1 H), 8.11 (d, J = 7.5 Hz, 1 H), 8.36 (d, J = 5.2 Hz, 1 H), 10.48 (s, 1 H). ¹³C NMR (63 MHz, CDCl₃): δ = 26.2, 26.7, 26.8, 28.4, 38.6, 72.6, 86.0, 88.2, 111.9, 114.1, 119.7, 121.5, 121.9, 128.4, 132.6, 133.0, 137.7, 142.9, 148.9. MS (EI, 70 eV): m/z (%) = 310 (17) [M⁺], 151 (24) [C₁₆H₁₅N₂O⁺], 209 (100) [C₁₄H₁₂N₂ ⁺], 182 (11) [C₁₀H₁₆NO₂ ⁺], 43(9) [C₂H₄O⁺]. UV/Vis (EtOH): λ_max (lg ε): 227 nm (4.09), 289 (4.03), 340 (3.57). C₁₉H₂₂N₂O₂ (310.4): Calcd C, 73.52; H, 7.14; N, 9.03. Found: C, 72.86; H, 7.11; N, 8.68.