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DOI: 10.1055/s-2003-36793
Vanadium(V)-Catalyzed Oxidation of (3R)-Linalool - The Selective Formation of Furanoid Linalool Oxides and their Conversion into Isocyclocapitelline Derivatives
Publication History
Publication Date:
22 January 2003 (online)
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
- 1
Phuong NM.Sung TV.Porzel A.Schmidt J.Merzweiler K.Adam G. Phytochemistry 1999, 52: 1725 - 2
Peng J.-N.Feng X.-Z.Zheng Q.-T.Liang X.-T. Phytochemistry 1997, 46: 1119 -
3a
Wüst M.Monsandl A. Eur. Food Res. Technol. 1999, 209: 3 -
3b
Winterhalter P.Katzenberger D.Schreier P. Phytochemistry 1986, 25: 1347 -
4a
Zhang JX.Wang G.-X.Xie P.Chen S.-F.Liang XT. Tetrahedron Lett. 2000, 41: 2211 -
4b
Wang GX.Zhang JX.Chen SF.Liang XT. Chin. Chem. Lett. 2001, 12: 199 -
4c
Mahboobi S.Koller M.Schollmeyer D. Monatsh. Chem. 2000, 131: 383 -
5a
Klein E.Farnow H.Rojahn W. Liebigs Ann. Chem. 1964, 675: 73 -
5b
Prileschajew N. Ber. Dtsch.Chem. Ges. 1909, 42: 4811 - 6
Villa de .De Vos DE.Montes de CC.Jacobs A. Tetrahedron Lett. 1998, 39: 8521 -
7a
Sams CK.Jørgensen KA. Acta Chim. Scand. 1995, 49: 839 -
7b
Sheldon RA. In The Chemistry of Functional Groups, PeroxidesPatai S. Wiley; Chichester: 1983. p.161-199 -
7c
Sharpless KB.Verhoeven TR. Aldrichimica Acta 1979, 12: 63 -
8a
Ohloff G.Giersch W.Schulte-Elte KH.Enggist P.Demole E. Helv. Chim. Acta 1980, 63: 1582 -
8b
Sharpless KB.Michaelson RC. J. Am. Chem. Soc. 1973, 6136 - 9
Sheldon RA. In Aspects of Homogeneous Catalysis Vol. 4:Ugo E. Reidel Publishing; Dordrecht: 1981. p.3-70 -
10a
González IC.Forsyth CJ. J. Am. Chem. Soc. 2000, 122: 9099 -
10b
Hashimoto M.Kan T.Nozaki K.Yanagiya M.Shirahama H.Matsumoto T. J. Org. Chem. 1990, 55: 5088 -
10c
Corey EJ.Ha D.-C. Tetrahedron Lett. 1988, 29: 3171 - 11
Hartung J.Greb M. J. Organometal. Chem. 2002, 661: 67 - 12
Mimoun H.Mignard M.Brechot P.Saussine L. J. Am. Chem. Soc. 1986, 108: 3711 - 13
Hartung J.Schmidt P. Synlett 2000, 367 - 15
Weinert B.Wüst M.Mosandl A.Hanssum H. Phytochem. Anal. 1998, 9: 10 -
17a
Castrette M.Axiotis GP. J. Organometal. Chem. 1981, 206: 139 -
17b
David L.Veschambre H. Tetrahedron Lett. 1984, 25: 543 - Tungsten-catalyzed oxidations:
-
19a
Sakaguchi S.Nishiyama Y.Ishii Y. J. Org. Chem. 1996, 61: 5307 -
19b
Villa de OAL.Sels BF.De Vos DE.Jacobs PA. J. Org. Chem. 1999, 64: 7267 - 20
Lempers HEB.Ripollès i Garcia A.Sheldon RA. J. Org. Chem. 1998, 63: 1408 - Titanium and titanium silicate-catalyzed oxidations:
-
21a
Schofield LJ.Kerton WJ.McMorn P.Bethell D.Ellwood S.Hutchings GJ. J. Chem. Soc., Perkin Trans. 2 2002, 1475 -
21b
Lattanzi A.Della Sala G.Russo M.Scettri A. Synlett 2001, 1479 -
21c
Corma A.Iglesias M.Sánchez F. J. Chem. Soc., Chemm. Commun. 1995, 1635 - 22
Felix D.Malera A.Seibl J.Kováts E. Helv. Chim. Acta 1963, 46: 1513 - 23
Yang D.Zhang C. J. Org. Chem. 2001, 66: 4814
References
Hartung, J.; Drees, S.; Greb, M.; Schmidt, P.; Svoboda, I.; Fuess, H.; Murso, A.; Stalke, D. Eur. J. Org. Chem., submitted.
16A 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); Rf cis-1 = 0.48; Rf 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 (mc, 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).
18Control experiments [14] indicated that vanadium(V) complex 4b catalyzes oxidation of racemic mixtures of chiral bishomoallylic alcohols without kinetic resolution.
24cis-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 (mc, 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): λmax (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 (mc, 1 H), 7.50 (mc, 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): λmax (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.
25
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 (mc, 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): λmax (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 (mc, 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): λmax (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.