1324
G. Hilt et al.
PAPER
Yield: 90 mg (0.49 mmol, 99%); colorless oil.
3 H), 1.98–2.04 (m, 4 H), 2.34–2.42 (m, 2 H), 4.32–4.37 (m, 1 H),
5.30 (s, 1 H), 5.32–5.38 (m, 2 H).
13C NMR (125 MHz, CDCl3): d = 14.1, 21.0, 22.7, 27.19, 27.21,
29.28, 29.31, 29.36, 29.46, 29.51, 29.8, 31.9, 34.5, 40.8, 79.3,
104.7, 129.8, 130.0, 174.3, 193.0 (resolved signals).
IR (Nujol): 3434, 3075, 2962, 2920, 1641, 1440, 1373, 1113, 1020,
972, 894 cm–1.
1H NMR (300 MHz, CDCl3): d = 0.94 (t, J = 7.5 Hz, 3 H), 1.43–
1.53 (m, 2 H), 1.57 (s, 3 H), 1.62 (s, 3 H), 1.66 (s, 3 H), 1.89 (s,
1 H), 1.98 (dd, J = 13.7, 9.4 Hz, 1 H), 2.16 (dd, J = 13.7, 3.4 Hz,
1 H), 2.68 (d, J = 15.4 Hz, 1 H), 2.79 (d, J = 15.5 Hz, 1 H), 3.56–
3.65 (m, 1 H), 4.80–4.85 (m, 2 H).
MS (EI): m/z (%) = 85 (18), 111 (100), 376 (3) [M]+.
HRMS (ESI): m/z calcd for C25H44O2: 376.3341; found: 376.3341.
13C NMR (75 MHz, CDCl3): d = 9.9, 18.2, 20.4, 20.5, 29.8, 41.1,
6-Methyl-2-[(10E)-nonadec-10-en-1-yl]-2,3-dihydro-4H-pyran-
4-one (15)
43.9, 70.2, 112.7, 124.7, 126.3, 144.8.
1H NMR (600 MHz, CDCl3): d = 0.88 (t, J = 7.0 Hz, 3 H), 1.20–
1.55 (m, 26 H), 1.61–1.67 (m, 1 H), 1.77–1.83 (m, 1 H), 1.94–1.98
(m, 4 H), 1.99 (s, 3 H), 2.33–2.42 (m, 2 H), 4.31–4.36 (m, 1 H),
5.30 (s, 1 H), 5.37–5.39 (m, 2 H).
MS (EI): m/z (%) = 93 (55), 109 (100), 121 (18), 135 (19), 149 (9),
182 (3) [M]+.
HRMS (EI): m/z calcd for C12H22O: 182.1671; found: 182.1678.
13C NMR (125 MHz, CDCl3): d = 14.1, 21.0, 22.7, 24.9, 29.16,
29.22, 29.35, 29.45, 29.48, 29.49, 29.63, 29.65, 31.9, 32.58, 34.5,
40.8, 79.3, 104.7, 130.3, 130.4, 174.3, 193.0 (resolved signals).
Hepialone (10)
1H NMR (300 MHz, CDCl3): d = 1.01 (t, J = 7.5 Hz, 3 H), 1.72–
1.90 (m, 2 H), 2.00 (s, 3 H), 2.37–2.41 (m, 2 H), 4.24–4.34 (m,
1 H), 5.31 (s, 1 H).
IR (KBr): 2924, 2854, 1672, 1613, 1398, 1336, 1261, 1096, 1031,
968, 805 cm–1.
MS (EI): m/z (%) = 85 (18), 111 (100), 376 (2) [M]+.
13C NMR (75 MHz, CDCl3): d = 9.2, 21.0, 27.5, 40.3, 80.4, 104.7,
174.2, 192.8.
The analytical data are consistent with the literature.9
HRMS (ESI): m/z calcd for C25H44O2: 376.3341; found: 376.3320.
2,3-Dimethyl-5-methylen-docosa-2,17-dien-7-ol (12)
The crude product was purified by column chromatography (pen-
tane–Et2O, 10:1).
References
(1) (a) Leading reference: Chem. Rev. 1997, 97, 2463–2706; this
special issue gives a comprehensive introduction into
biochemical and biological aspects of polyketides. (b) See
also: Sattely, E. S.; Fischbach, M. A.; Walsh, C. T. Nat.
Prod. Rep. 2008, 25, 757.
(2) For a comprehensive review, see: Hilt, G.; Weske, D. F.
Chem. Soc. Rev. 2009, 38, 3082.
(3) Birch, A. J. J. Chem. Soc. 1944, 430.
(4) Tung, J. C.; Chen, M. W.; Noll, B. C.; Taylor, R. E.; Fields,
S. C.; Dent, W. H. III; Green, F. R. III Synthesis 2007, 2388.
(5) (a) Hilt, G.; Janikowski, J.; Hess, W. Angew. Chem. Int. Ed.
2006, 45, 5206. (b) Hilt, G.; Janikowski, J. Org. Lett. 2009,
11, 774.
(6) (a) Hilt, G.; du Mesnil, F.-X.; Lüers, S. Angew. Chem. Int.
Ed. 2001, 40, 387. (b) Hilt, G.; Lüers, S. Synthesis 2002,
609. (c) Hilt, G.; Lüers, S.; Schmidt, F. Synthesis 2003, 634.
(7) Ligands such as 2,4,6-trimethyl-N-(pyridin-2-ylmethyl-
ene)aniline (as a representative of a pyridine-imine-type
ligand) as well as N,N'-dibutylethane-1,2-diimine or N,N'-
dicyclohexylethane-1,2-diimine (diimine-type ligands) can
be applied.
Yield: 122 mg (0.34 mmol, 84%); colorless oil.
IR (Nujol): 3376, 2925, 2855, 1641, 1463, 894, 721 cm–1.
1H NMR (300 MHz, CDCl3): d = 0.86–0.93 (m, 3 H), 1.24–1.51 (m,
20 H), 1.60 (s, 3 H), 1.64 (s, 3 H), 1.69 (s, 3 H), 1.77 (s, 1 H), 1.97–
2.04 (m, 5 H), 2.18 (dd, J = 13.7, 3.2 Hz, 1 H), 2.70 (d, J = 15.4 Hz,
1 H), 2.81 (d, J = 15.4 Hz, 1 H), 3.65–3.73 (m, 1 H), 4.83–4.86 (m,
2 H), 5.32–5.36 (m, 2 H).
13C NMR (75 MHz, CDCl3): d = 14.0, 18.3, 20.5, 20.6, 22.3, 25.7,
26.9, 27.2, 29.3, 29.5, 29.57, 29.60, 29.7, 29.8, 32.0, 37.1, 41.1,
44.5, 68.8, 112.9, 124.7, 126.5, 129.8, 129.9, 144.8.
MS (EI): m/z (%) = 95 (30), 109 (100), 124 (44), 135 (50), 149 (21),
163 (10), 179 (5), 191 (4), 220 (3), 237 (5), 277 (2), 301 (6), 319 (7),
344 (6), 362 (8) [M]+.
HRMS (EI): m/z calcd for C25H46O: 362.3549; found: 362.3558.
10-(6-Methyl-4-oxo-3,4-dihydro-2H-pyran-2-yl)decanal (13)
The crude product was purified by column chromatography (pen-
tane–Et2O, 1:2).
(8) (a) For 7a, see: Axenrod, T.; Mangiaracina, P.; Watnick, C.
M.; Wieder, M. J.; Bulusu, S. Org. Magn. Reson. 1980, 13,
197. (b) For 7b, see: Alberola, A.; Andres, C.;
Gonzalez Ortega, A.; Pedrosa, R. J. Heterocycl. Chem.
1984, 21, 1575.
(9) (a) Rao, B. V.; Rao, A. S. Synth. Commun. 1995, 25, 1531.
(b) Kubo, I.; Matsumoto, T.; Wagner, D. L. Tetrahedron
Lett. 1985, 26, 563.
(10) (a) MacDonald, F. K.; Burnell, D. J. J. Org. Chem. 2009, 74,
6973. (b) Wang, H.; Shuhler, B. J.; Xian, M. J. Org. Chem.
2007, 72, 4280. (c) Zhang, J.; Li, Y.; Wang, W.; She, X.;
Pan, X. J. Org. Chem. 2006, 71, 2918. (d) Calad, S. A.;
Ćiraković, J.; Woerpel, K. A. J. Org. Chem. 2006, 72, 1027.
(e) Jin, M.; Taylor, R. E. Org. Lett. 2005, 7, 1303.
(11) Ramaroson-Raonizafinimanana, B.; Gaydou, E. M.;
Bombarda, I. J. Agric. Food Chem. 1999, 47, 3202.
(12) For the generation of oxygen-free ozone, see experimental
section and: Schutt, W. S.; Sigman, M. E.; Li, Y. Anal. Chim.
Acta 1996, 319, 369.
Yield: 36 mg (0.14 mmol, 40%); colorless oil.
IR (Nujol): 3463, 2926, 1703, 1666, 1618, 1454, 1397, 1337, 996,
835, 693 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.27–1.88 (m, 16 H), 1.99 (s,
3 H), 2.35–2.46 (m, 4 H), 4.29–4.39 (m, 1 H), 5.31 (s, 1 H), 9.77 (s,
1 H).
13C NMR (75 MHz, CDCl3): d = 21.0, 22.0, 24.8, 29.1, 29.27,
29.30, 29.35, 34.4, 40.8, 43.9, 79.3, 104.7, 174.3, 193.0, 202.7.
MS (EI): m/z (%) = 85 (100), 111 (87), 125 (5), 139 (4), 223 (11),
265 (3) [M+ – 1].
HRMS (ESI): m/z calcd for C16H26O3Na+: 289.1780, found:
289.1774.
6-Methyl-2-[(10Z)-nonadec-10-en-1-yl]-2,3-dihydro-4H-pyran-
4-one (14)
IR (KBr): 2924, 2854, 1672, 1614, 1398, 1336, 1033, 808, 723 cm–1.
1H NMR (600 MHz, CDCl3): d = 0.88 (t, J = 7.0 Hz, 3 H), 1.22–
1.50 (m, 26 H), 1.61–1.67 (m, 1 H), 1.77–1.83 (m, 1 H), 1.99 (s,
Synthesis 2010, No. 8, 1321–1324 © Thieme Stuttgart · New York