8916
E. Alvarez-Manzaneda et al. / Tetrahedron 67 (2011) 8910e8917
syrup (15% ether/hexanes), ½a D25
ꢁ
þ70.9 (c 0.6, CHCl3). 1H NMR
(CH2), 39.5 (CH2), 42.1 (CH2), 56.19.(CH), 60.3 (CH), 79.5 (C), 91.6
(CDCl3, 500 MHz)
d
: 0.71 (s, 3H), 0.76 (s, 3H), 0.78 (s, 3H), 1.06 (ddd,
(CH), 169.7 (C); IR (film) 1744, 1456, 1384, 1260, 1018, 800 cmꢂ1
.
J¼13.4, 13.4, 4.1 Hz, 1H), 1.15 (s, 3H), 1.16e1.65 (m, 14H), 1.95 (ddd,
J¼10.7, 8.3, 1.5 Hz, 1H), 2.04 (br s, 1H), 2.49 (m, 1H), 3.33 (dd, J¼10.9,
9.0 Hz, 1H), 3.43 (dd, J¼11.0, 4.0 Hz, 1H), 4.24 (m, 1H), 4.74 (s, 1H),
HRMS (EI) Mþ m/z: calcd for C20H34O3 322,2508, found: 322,2514.
4.4.32. (5aR,7aS,11aS,11bR)-4-Acetoxy-5a,8,8,11a-tetramethyl-3-
methylenetetradecahydronaphtho[2,1-b]oxepine (6e) and 4-((1R,
2R,5aR,8aS)-2-hydroxy-2,5,5,8a-tetramethyldecahydronaphthalen-1-
yl)-2-methylenebutanal (6f). Compounds 6e and 6f were obtained
as a mixture in a 1:1 ratio.
4.58 (s,1H); 13C NMR (CDCl3,125 MHz)
d: 16.1 (CH2) 18.8 (CH2), 20.4
(CH2), 21.5 (CH3), 22.7 (CH2), 23.8 (CH3), 30.6 (CH2), 33.4 (C), 33.5
(CH3), 38.3 (C), 39.0 (CH2), 40.4 (CH2), 42.0 (CH2), 53.4 (CH), 56.3
(CH), 66.2 (CH2), 72.8 (CH), 106.9 (CH2), 150.9 (C); IR (film): 3461,
1643, 1454, 1412, 1095, 1041, 888, 756 cmꢂ1. HRMS (EI) Mþ m/z:
calcd for C20H34O2 306,2559, found: 306,2559.
Compound 6e. Colorless syrup (5% ether/hexanes). 1H NMR
(CDCl3, 500 MHz) signals assignable to the major isomer d: 0.71 (s,
6H), 0.79 (s, 3H), 0.75e0.90 (m, 2H), 1.15e1.37 (m, 4H), 1.25 (s, 3H),
1.54e1.66 (m, 13H), 2.05 (s, 3H), 2.47 (ddd, J¼13.0, 6.6, 3.7 Hz, 1H),
4.89 (s, 1H), 4.90 (s, 1H), 6.35 (s, 1H); 13C NMR (CDCl3, 125 MHz)
4.4.28. 2-Acetoxytetrahydro-2H-pyran (6a). Colorless oil. 1H NMR
(CDCl3, 500 MHz)
d
: 1.52 (m, 1H), 1.61e1.67 (m, 1H), 1.76 (dt, J¼9.7,
3.1 Hz, 1H), 1.80 (dd, J¼9, 2 Hz, 1H), 1.84 (t, J¼5.0 Hz, 1H), 2.08 (d,
J¼2.0 Hz, 1H), 2.09 (s, 3H), 3.89 (ddd, J¼11.3, 9, 3.1 Hz, 1H), 3.60 (dd,
signals assignable to the major isomer d: 15.6 (CH3), 18.7 (CH2), 19.9
(CH2), 21.4 (CH3), 21.5 (CH3), 22.2 (CH3), 33.2 (CH2), 33.3 (CH3), 33.4
(C), 38.3 (C), 40.0 (CH2), 41.7 (CH2), 42.3 (CH2), 55.9 (CH), 59.1 (CH),
81.9 (C), 92.7 (CH), 110.8 (CH2), 148.2 (C), 169.6 (C); IR (film): 2936,
1733, 1650, 1452, 1386, 1242, 1132, 994, 934, 756 cmꢂ1. HRMS (EI)
Mþ m/z: calcd for C21H34O3 334,2508, found: 334,2519.
J¼11.5, 4.9 Hz,1H), 5.93 (t, J¼3 Hz,1H); 13C NMR (CDCl3,125 MHz)
d:
18.7 (CH2), 21.2 (CH3), 24.9 (CH2), 29.2 (CH2), 63.4 (CH2), 92.7 (CH),
169.8 (C).
4.4.29. (3aR,5aS,9aS,9bR)-2-Acetoxy-3a,6,6,9a-Tetramethyldodeca-
Compound 6f. Colorless syrup (20% ether/hexanes), ½a D
ꢁ þ20.4
hydronaphtho[2,1-b]furan (6b). Colorless syrup (5% ether/hexanes).
(c 1.0, CHCl3), 1H NMR (CDCl3, 500 MHz)
d
: 0.75 (s, 3H), 0.76 (s, 3H),
1H NMR (CDCl3, 500 MHz)
d: 0.81 (s, 3H), 0.81 (s, 3H), 0.82 (s, 3H),
0.85 (s, 3H), 0.90 (dd, J¼12.2, 2.2 Hz, 1H), 0.94 (dd, J¼12.8, 12.8,
3.6 Hz, 1H), 1.09 (t, J¼3.9 Hz, 1H), 1.12 (s, 3H), 1.22 (ddd, J¼13.4, 13.4,
3.2 Hz,1H),1.25 (ddd, J¼13.4,13.4, 3.1 Hz,1H),1.30e1.8 (m, 9H),1.84
(dt, J¼12.3, 3.3 Hz, 1H), 2.2e2.40 (m, 2H), 5.95 (s, 1H), 6.30 (s, 1H),
0.85 (s, 3H), 0.86 (s, 3H), 0.86 (s, 3H), 0.89e2.07 (m, 24H), 1.12 (s,
3H), 1.24 (s, 3H), 2.02 (s, 3H), 2.03 (s, 3H), 2.09e2.20 (m. 2H), 6.19
(dd, J¼11.7, 5.8 Hz, 2H); 13C NMR (CDCl3, 125 MHz)
d: 15.1 (CH3),
15.3 (CH3), 18.2 (CH2), 18.3 (CH2), 20.4 (CH2), 20.9 (CH2), 21.0 (CH3),
21.4 (CH3), 22.8 (CH3), 23.0 (CH3), 30.0 (CH2), 30.3 (CH2), 33.0 (C),
33.1 (C), 33.4 (CH3), 33.5 (CH3), 36.0 (C), 36.1 (C), 39.5 (CH2), 39.6
(CH2), 39.9 (CH2), 40.0 (CH2), 42.3 (CH2), 42.4 (CH2), 56.6 (CH),
56.97 (CH), 57.0 (CH), 60.0 (CH), 82.9 (C), 84.3 (C), 97.4 (CH), 98.6
(CH), 170.4 (C), 170.7 (C); IR (film): 1743, 1588, 1461, 1380, 1238,
1219, 1121, 1082, 1042, 969 cmꢂ1. HRMS (EI) Mþ m/z: calcd for
C18H30O3 294,2195, found: 294,2204.
9.50 (s, 1H); 13C NMR (CDCl3, 125 MHz)
d: 15.4 (CH2), 18.4 (CH2),
20.4 (CH2), 21.4 (CH3), 23.9 (CH2), 24.0 (CH3), 26.9 (CH3), 31.5 (CH2),
33.2 (C), 33.3 (CH3), 38.9 (C), 39.6 (CH2), 41.9 (CH2), 44.2 (CH2), 56.1
(CH), 61.6 (CH), 74.0 (C), 134.0 (CH2), 150.9 (C), 195.0 (CH). IR (film):
3457, 1687, 1650, 1461, 1387, 1124, 939, 756 cmꢂ1. HRMS (EI) Mþ m/
z: calcd for C19H32O2 292,2402, found: 292,2395.
Acknowledgements
4.4.30. (3aR,5S,5aS,9aS,9bR)-2,5-Diacetoxy-3a,6,6,9a-tetrame-
The authors thank the Spanish Ministry of Science and In-
novation (Project CTQ2009-09932) and the Regional Government
of Andalucia (Project P07-FQM-03101 and assistance to the FQM-
348 group) for financial support. H.B. thanks the Spanish Agency
for the International Cooperation and Development (AECID) for the
predoctoral grant provided.
thyldodecahydronaphtho[2,1-b]furan (6c). Major isomer: colorless
syrup (15% ether/hexanes), ½a D25
ꢁ
þ16.6 (c 0.8, CHCl3). 1H NMR
(CDCl3, 500 MHz) d: 0.88 (s, 3H), 0.92 (s, 3H), 0.99 (s, 3H), 1.23 (s,
3H), 1.10e1.90 (m, 11H), 2.03 (s, 3H), 2.04 (s, 3H), 2.18 (ddd, J¼11.1,
11.1, 4.1 Hz, 1H), 2.20 (dd, J¼11.0, 4.0 Hz, 1H), 5.17 (ddd, J¼11.1, 11.1,
4.1 Hz, 1H), 6.23 (d, J¼5.5 Hz, 1H); 13C NMR (CDCl3, 125 MHz)
d: 16.6
(CH3), 18.1 (CH2), 21.5 (CH3), 21.8 (CH3), 22.0 (CH3), 24.1 (CH3), 30.3
(CH2), 33.4 (C), 35.4 (C), 35.8 (CH3), 39.9 (CH2), 43.7 (CH2), 47.1
(CH2), 56.6 (CH), 59.4 (CH), 71.5 (CH), 82.4 (C), 97.5 (CH), 170.1 (C),
References and notes
170.4 (C); IR (film): 1737, 1459, 1377, 1240, 1033, 974 cmꢂ1
.
1. For some representative examples, see: (a) Brock, M. L.; Kepner, R. E.; Webb, A.
D. Am. J. Enol. Vitic. 1980, 35, 151e155; (b) Bel-Rhlid, R.; Fauve, A.; Veschambre,
H. J. Org. Chem. 1989, 54, 3221e3223; (c) Shi, X.; Leal, W. S.; Meinwald, J. Bioorg.
Med. Chem. 1996, 4, 297e303; (d) Neuser, F.; Richter, U.; Berger, R. G. Leb-
ensmittelchemie 1999, 53, 4e6; (e) Andrus, M. B.; Hicken, E. J.; Stephens, J. C.;
Bedke, D. K. J. Org. Chem. 2006, 71, 8651e8654.
Minor isomer: colorless syrup (10% ether/hexanes), ½a D
ꢁ þ51.7 (c
0.9, CHCl3). 1H NMR (CDCl3, 500 MHz)
d
: 0.88 (s, 3H), 0.97 (s, 3H),
0.99 (s, 3H), 1.07 (ddd, J¼12.8, 12.8, 4.0 Hz, 1H), 1.26 (m, 1H), 1.35 (s,
3H), 1.32e1.50 (m, 4H), 1.50e1.75 (m, 4H), 1.82 (ddd, J¼13.8, 12.6,
5.0 Hz, 1H), 2.04 (s, 3H), 2.05 (s, 3H), 2.14e2.23 (m, 2H), 5.15 (ddd,
J¼11.0,11.0, 4.0 Hz,1H), 6.22 (dd, J¼6.2, 5.1 Hz,1H); 13C NMR (CDCl3,
2. Nakata, T.; Tanaka, T.; Oishi, T. Tetrahedron Lett. 1983, 24, 2653e2656.
3. Larcheveque, M.; Petit, Y. Bull. Soc. Chim. Fr. 1989, 130e139.
ꢀ
4. Paterson, I.; Wallace, D. J.; Velazquez, S. M. Tetrahedron Lett.1994, 35, 9083e9086.
125 MHz) d: 16.4 (CH3), 18.1 (CH2), 21.4 (CH3), 21.8 (CH3), 22.0 (CH3),
5. (a) Solsona, J. G.; Romea, P.; Urpí, F. Tetrahedron Lett. 2004, 45, 5379e5382; (b)
Lorente, A.; Pellicena, M.; Romea, P.; Urpí, F. Tetrahedron Lett. 2010, 51, 942e945.
6. Palomo, C.; Aizpurua, J. M.; García, J. M.; Galarza, R.; Legido, M.; Urchagi, R.;
24.3 (CH3), 30.0 (CH2), 33.4 (C), 35.6 (C), 35.8 (CH3), 39.7 (CH2), 43.7
(CH2), 46.7 (CH2), 59.5 (CH), 59.8 (CH) 71.2 (CH), 81.2 (C), 98.6 (CH),
ꢀ
ꢀ
Roman, P.;Luque, A.;Server-Carrio, J.;Linden, A. J. Org. Chem.1997, 62, 2070e2079.
7. Afonso, C. A. M.; Barros, M. T.; Godinho, L. S.; Maycock, C. D. Tetrahedron 1993,
49, 4283e4292.
170.1 (C), 170.7 (C); IR (film): 1746, 1457, 1365, 1240, 1030, 965 cmꢂ1
.
HRMS (EI) Mþ m/z: calcd for C20H32O5 352,225, found: 352,231.
8. For some representative articles, see: (a) Drummond, A. V.; Waters, W. A. J.
Chem. Soc. 1955, 497e504; (b) Littler, J. S. J. Chem. Soc. 1962, 822e827; (c)
Rawlison, D. J.; Sosnovsky, G. Synthesis 1973, 567e603.
9. (a) Mizukami, F.; Ando, M.; Tanaka, T.; Imamura, J. Bull. Chem. Soc. Jpn. 1978,
335e336; (b) Koser, G. F.; Relenyi, A. G.; Kalos, A. N.; Rebovic, L.; Wettach, R. M.
J. Org. Chem. 1982, 47, 2487e2489; (c) Lodaya, J. S.; Koser, G. F. J. Org. Chem. 1988,
53, 210e212.
10. Irie, H.; Ketakawa, J.; Tomita, M.; Mizuno, Y. Chem. Lett. 1981, 637e640 and
references cited therein.
11. (a) Vedejs, E. J. Am. Chem. Soc. 1974, 96, 5944e5946; (b) Vedejs, E.; Engler, D. A.;
Telschov, J. E. J. Org. Chem. 1978, 43, 188e196; (c) Chen, B. C.; Zhou, P.; Davis, F. A.;
Ciganek, E. Organic Reactions; John Wiley & Sons: New York, 2003; 62; 1e356.
4.4.31. (5aR,7aS,11aS,11bR)-4-Acetoxy-5a,8,8,11a-tetramethylte-
tradecahydronaphtho[2,1-b]oxepine (6d). Colorless syrup (3% ether/
hexanes). 1H NMR (CDCl3, 500 MHz) signals assignable to the major
isomer
d
: 0.71 (s, 6H); 0.79 (s, 3H); 1.07 (ddd, J¼13.4, 13.4; 4.0 Hz,
1H); 1.16 (s, 3H); 1.98 (s, 3H), 1.21e1.81 (m, 14H), 6.03 (dd, J¼9.6,
2.0 Hz, 1H, 2H), 13C NMR (CDCl3, 125 MHz) signals assignable to the
major isomer
d: 16.2 (CH3), 18.66 (CH2), 20.97 (CH2), 21.3 (CH3), 21.6
(CH3), 22.2 (CH2) 24.1 (CH3), 26.6 (CH2), 33.4 (CH3), 35.5 (CH2), 39.17