M. Sono et al. / Tetrahedron 64 (2008) 11096–11104
11103
(calcd for C13H22O2 210.1620); IR 3380, 1690 cmꢁ1
;
1H NMR
1700 cmꢁ1
;
1H NMR (600 MHz, CDCl3)
d
1.04 (3H, d, J¼6.6 Hz),
(600 MHz, CDCl3) 0.80 (3H, s), 1.21 (3H, s), 1.36 (1H, m), 1.43–1.52
d
1.17–1.76 (11H, m), 1.86 (1H, m), 1.95–2.03 (2H, m), 2.26 (1H,
m), 2.38 (1H, m), 2.43 (2H, td, J¼7.2, 1.9 Hz), 9.76 (1H, t,
J¼1.9 Hz).
(3H, m), 1.66 (1H, m), 1.68 (1H, m), 1.74 (1H, m), 1.80 (1H, m), 1.93
(1H, m), 2.01 (1H, m), 2.14 (1H, m), 2.16 (1H, m), 2.29 (1H, m), 2.34
(1H, m), 2.69 (1H, d, J¼10.2 Hz); 13C NMR (150 MHz, CDCl3)
d 17.2
(CH3), 20.3 (CH2), 21.5 (CH2), 22.4 (CH2), 24.5 (CH2), 28.2 (CH3), 32.8
(CH2), 36.8 (CH2), 41.9 (CH2), 49.2 (C), 55.4 (CH), 77.3 (CH), 214.6 (C).
4.1.21. 3-Methyl-2-(6-hydroxyhexyl)cyclohex-2-enone (33)
Oil; MS (EI) m/z 210 (Mþ), 195 (base), 177, 151, 137, 124, 96, 79,
67; HRMS (EI) found m/z 210.1626 (calcd for C13H22O2 210.1620); IR
4.1.15. 3-Methyl-2-(5-oxohexyl)cyclohexanone (26)
3450,1680, 1620 cmꢁ1; 1H NMR (200 MHz, CDCl3)
d 1.25–1.75 (10H,
MS (EI) m/z 210 (Mþ), 192, 177, 153, 112, 97 (base), 81, 69; HRMS
(EI) found m/z 210.1600 (calcd for C13H22O2 210.1620); IR
m), 1.95 (3H, s), 2.21–2.40 (6H, m), 3.39 (1H, td, J¼6.6, 1.0 Hz), 3.61
(2H, t, J¼6.6 Hz).
1710 cmꢁ1; 1H NMR (600 MHz, CDCl3)
d
1.04 (3H, d, J¼6.6 Hz), 1.19
(1H, m), 1.31 (1H, m), 1.40–1.72 (7H, m), 1.86 (1H, m), 1.96–2.03 (2H,
m), 2.14 (3H,s), 2.26 (1H, dddd, J¼13.2, 11.4, 5.4, 1.3 Hz), 2.36 (1H,
dtd, J¼13.2, 4.8, 1.4 Hz), 2.43 (2H, t, J¼7.4 Hz); 13C NMR (50 MHz,
4.1.22. 3-Methyl-2-(6-hydroxyhexyl)cyclohexanone (34)
Oil; MS (EI) m/z 212 (Mþ), 169, 151, 125, 112, 97 (base), 84;
HRMS (EI) found m/z 212.1756 (calcd for C13H24O2 212.1777); IR
CDCl3)
d
20.5 (CH3), 24.1 (CH2), 25.6 (CH2), 26.5 (CH2), 26.8 (CH2),
3400, 1700 cmꢁ1 1H NMR (600 MHz, CDCl3)
; d 1.04 (3H, d,
29.9 (CH3), 33.2 (CH2), 38.4 (CH), 41.6 (CH2), 43.6 (CH2), 57.2 (CH),
209.4 (CO), 213.2 (CO).
J¼6.6 Hz), 1.21 (1H, m), 1.24–1.38 (5H, m), 1.44 (1H, m), 1.49 (1H,
m), 1.54–1.59 (2H, m), 1.61–1.74 (3H, m), 1.87 (1H, m), 1.97 (1H,
m), 1.99 (1H, m), 2.26 (1H, dddd, J¼13.5, 9.0, 6.0, 1.2 Hz), 2.37
(1H, dtd, J¼13.5, 4.8, 1.2 Hz), 3.64 (2H, t, J¼6.6 Hz); 13C NMR
4.1.16. 3-Methyl-2-(5-oxohexyl)cyclohex-2-en-1-ol (27)
MS (CI) m/z 209 (MꢁH)þ, 193 (base), 175, 135, 111, 93, 81, 55;
(150 MHz, CDCl3) d 20.5 (CH3), 25.4 (CH2), 25.5 (CH2), 26.9 (CH2),
HRMS (CI) found m/z 209.1516 (MꢁH)þ (calcd for C13H21O2
27.3 (CH2), 29.7 (CH2), 32.7 (CH2), 33.0 (CH2), 38.3 (CH), 41.4
(CH2), 57.4 (CH), 63.0 (CH2), 213.4 (C).
209.1542); IR 3440, 1710 cmꢁ1 1H NMR (300 MHz, CDCl3)
; d 1.26–
1.69 (9H, m), 1.63 (3H, s), 1.93 (2H, br s), 2.14 (3H, s), 2.20–2.48 (2H,
m), 2.45 (2H, t, J¼15.0 Hz), 4.03 (1H, br s); 13C NMR (75 MHz, CDCl3)
Acknowledgements
d
17.9 (CH2), 19.2 (CH3), 24.0 (CH2), 28.5 (CH2), 29.9 (CH3), 30.1
(CH2), 32.0 (CH2), 32.2 (CH2), 43.7 (CH2), 67.4 (CH), 131.9 (C), 132.0
(C), 209.3 (C).
We thank Dr. Masami Tanaka and Miss Yasuko Okamoto,
Tokushima Bunri University, for measurement of 600 MHz NMR
and MS spectra, respectively. This study was financially supported
in part by a MEXT.HAITEKU, 2003–2007.
4.1.17. 2-(5-Hydroxyhexyl)-3-methyl-2-cyclohex-1-enone (28)
MS (EI) m/z 210 (Mþ), 195, 177, 163, 151, 135 (base), 124, 96,
79, 67; HRMS (EI) found m/z 210.1613 (calcd for C13H22O2
210.1619); IR 3450, 1660, 1620 cmꢁ1 1H NMR (300 MHz, CDCl3)
;
Supplementary data
d
1.18 (3H, d, J¼6.3 Hz), 1.25–1.70 (8H, m), 1.93 (3H, s), 1.88–1.97
(2H, m), 2.25–2.40 (5H, m), 3.79 (1H, sextet, J¼6.3 Hz); 13C NMR
Experimental procedures for preparation of the substrates 1–6,
X-ray ORTEP figures as well as several parameters of compounds 25
and 29, NOE correlations of compounds 11,13–16, 18–20, 22, and 23,
and 1H NMR and 13C NMR spectra of all new compounds have been
included. Supplementary data 1 and 2 associated with this article
can be found in the online version. Supplementary data associated
with this article can be found in the online version, at doi:10.1016/
(75 MHz, CDCl3)
d 21.2 (CH3), 22.3 (CH2), 23.5 (CH3), 25.1 (CH2),
25.9 (CH2), 29.1 (CH2), 32.8 (CH2), 37.9 (CH2), 39.1 (CH2), 68.1
(CH), 135.7 (C), 155.3 (C), 198.9 (C).
4.1.18. (1S
*
,2S
*
,8S )-2-Hydroxy-1-methylbicyclo[6.4.0]dodecan-9-
*
one (29)
Crystal; mp 105–107 ꢀC (hexane–EtOAc); MS (EI) m/z 210 (Mþ),
195, 177, 167, 149, 125, 119, 111 (base), 97; HRMS (EI) found m/z
210.1613 (calcd for C13H22O2 210.1619); IR 3440, 1690 cmꢁ1 1H
;
References and notes
NMR (600 MHz, CDCl3)
d 0.88 (3H, s), 1.40–1.46 (3H, m), 1.54–1.92
(11H, m), 2.18 (1H, ddd, J¼13.7, 4.6, 1.9 Hz), 2.34 (1H, dd, J¼5.4,
1. Girard, P.; Namy, L. J.; Kagan, H. B. J. Am. Chem. Soc. 1980, 102, 2693.
2. Molander, G. A. Chem. Rev. 1992, 92, 29.
3. Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307.
4. Little, R. D. Chem. Rev. 1996, 96, 93.
1.5 Hz), 2.44 (1H, td, J¼13.7, 6.9 Hz), 3.84 (1H, dd, J¼7.2, 2.4 Hz); 13C
NMR (150 MHz, CDCl3)
d 16.3 (CH3), 21.4 (CH2), 24.9 (CH2), 26.1
(CH2), 26.7 (CH2), 29.4 (CH2), 29.8 (CH2), 33.9 (CH2), 37.2 (CH2), 43.6
(C), 58.0 (CH), 75.2 (CH), 215.0 (C).
5. Sono, M.; Onishi, S.; Tori, M. Tetrahedron 2003, 59, 3385.
6. Sono, M.; Shoji, T.; Tamaki, T.; Kishi, S.; Tori, M. Heterocycles 2007, 72, 517.
7. Sono, M.; Hashimoto, A.; Nakashima, K.; Tori, M. Tetrahedron Lett. 2000,
41, 5115.
8. Sono, M.; Nakashiba, Y.; Nakashima, K.; Tori, M. J. Org. Chem. 2000, 65, 3099.
9. (a) Kagan, H. B.; Namy, J. L.; Girard, P. Tetrahedron 1981, 37, 175; (b) Curran, D. P.;
Fevig, T. L.; Totleben, M. J. Synlett 1990, 773; (c) Curran, D. P.; Gu, X.; Zhang, W.;
Dowd, P. Tetrahedron 1997, 53, 9023; (d) Hansen, A. M.; Linfsay, K. B.; An-
tharjanam, P. K. S.; Karaffa, J.; Daasbjerg, K.; Flowers, R. A., II; Skrydstrup, T.
J. Am. Chem. Soc. 2006, 128, 9616.
4.1.19. 6-(6-Hydroxy-2-methylcyclohex-1-enyl)hexanal (31)
Oil; MS (CI) m/z 211 (MþH)þ, 210, 209, 194, 193 (base), 175,
111; HRMS (CI) found m/z 209.1529 (MꢁH)þ (calcd for C13H21O2
209.1542); IR 3400, 1720 cmꢁ1
;
1H NMR (600 MHz, CDCl3)
d
1.26 (1H, m), 1.35 (1H, m), 1.42 (2H, m), 1.55–1.68 (5H, m),
10. cf. Sato, A.; Masuda, T.; Arimoto, H.; Uemura, D. Org. Biomol. Chem. 2005, 3,
2231.
11. (a) Herz, W.; Watanabe, H.; Miyazaki, M.; Kishida, Y. J. Am. Chem. Soc. 1962, 84,
2601; (b) Emerson, M. T.; Herz, W.; Caughlan, C. N.; Witters, R. W. Tetrahedron
Lett. 1966, 6151.
1.63 (3H, s), 1.77 (1H, m), 1.79 (1H, m), 1.94 (2H, m), 2.13 (1H,
m), 2.16 (1H, m), 2.43 (2H, td, J¼7.4, 1.6 Hz), 4.03 (1H, br s),
9.77 (1H, t, J¼1.6 Hz); 13C NMR (150 MHz, CDCl3)
d 17.8 (CH2),
19.2 (CH3), 22.0 (CH2), 28.7 (CH2), 29.4 (CH2), 30.1 (CH2), 31.9
(CH2), 32.2 (CH2), 43.9 (CH2), 67.3 (CH), 131.8 (C]), 132.1
(CH]), 202.9 (CO).
12. Ayer, W. A.; Lee, S. P. Can. J. Chem. 1979, 57, 3332.
13. (a) Snider, B. B.; Vo, N. H.; O’Neil, S. V.; Foxman, B. M. J. Am. Chem. Soc. 1996, 118,
7644; (b) Tori, M.; Toyoda, N.; Sono, M. J. Org. Chem. 1998, 63, 306; (c) Naka-
shima, K.; Fujisaki, N.; Inoue, K.; Minami, A.; Nagaya, C.; Sono, M.; Tori, M. Bull.
Chem. Soc. Jpn. 2006, 79, 1955.
4.1.20. 6-(6-Methyl-2-oxocyclohexyl)hexanal (32)
14. (a) Molander, G. A.; George, K. M.; Monovich, L. G. J. Org. Chem. 2003, 68, 9533;
Oil; MS (EI) m/z 210 (Mþ), 167, 125, 112, 97 (base); HRMS (EI)
found m/z 210.1628 (calcd for C13H22O2 210.1620); IR
´
¨
(b) Monovich, L. G.; Huerou, Y. L.; Ronn, M.; Molander, G. A. J. Am. Chem. Soc.
2000, 122, 52; (c) Molander, G. A.; McKie, J. A. J. Org. Chem. 1994, 59, 3186.