Preparation of Oxepanes, Oxepenes, and Oxocanes
J . Org. Chem., Vol. 61, No. 17, 1996 5799
(3Z,6E)-3,6-Octadien -1-ol (10b). Ten percent of the (3Z,6Z)-
isomer was present, due to the isomeric purity of the com-
mercial crotonyl chloride: 1H NMR (250 MHz, CDCl3) δ 1.67
(dd, J ) 0.5, 6.5 Hz, 3H), 2.20 (s, 1H), 2.36 (q, J ) 6.5 Hz,
2H), 2.79 (t, J ) 6.5 Hz, 2H), 3.66 (t, J ) 6.5 Hz, 2H), 5.32-
5.66 (m, 4H); MS EI m/ z (rel inten) 108 (7), 98 (21), 97 (11),
95 (23), 93 (85), 83 (13), 82 (41), 81 (38), 80 (26), 79 (37), 77
(61), 67 (100), 66 (17), 65 (17), 55 (89), 53 (44), 41 (62). Anal.
Calcd for C8H14O: C, 76.14; H, 11.18. Found: C, 76.37; H,
11.21.
2.15-2.30 (m, 1H), 2.36-2.54 (m, 2H), 2.68 (ddt, J ) 5.2, 8.5,
15.0 Hz, 1H), 2.93 (dt, J ) 3.8, 6.3 Hz, 1H), 3.92 (dt, J ) 2.5,
8.5 Hz, 1H), 4.18 (q, J ) 8.5 Hz, 1H), 4.48 (m, 1H), 5.40 (dtq,
J ) 1.0, 6.3, 15.0 Hz, 1H), 5.67 (dq, J ) 6.3, 15 Hz, 1H); 13C
NMR δ 18.0, 33.9, 39.0, 40.6, 66.1, 81.8, 125.9, 128.5; MS EI
m/ z (rel inten) 252 (1), 197 (28), 70 (100), 55 (22). Anal. Calcd
for C8H13IO: C, 38.12; H, 5.20. Found: C, 38.28; H, 5.40.
(2R*,3R*)-3-Iod o-2-m eth yl-4-oxocen e (16): 1H NMR (200
MHz, CDCl3) δ 1.94 (d, J ) 7.8 Hz, 3H), 2.10-2.60 (m, 4H),
2.92 (m, 1H), 3.50 (td, J ) 1.0, 10.5 Hz, 1H), 4.05-4.20 (m,
2H), 5.78 (m, 2H); 13C NMR δ 12.5, 24.9, 32.0, 36.4, 69.8, 84.0,
128.1, 130.7. Anal. Calcd for C8H13IO: C, 38.12; H, 5.20.
Found: C, 38.51; H, 5.41.
(2R*,3R*)-2-[2(Z)-Bu ten yl]-3-iod otetr a h yd r ofu r a n (17):
1H NMR (200 MHz, CDCl3) δ 1.65 (d, J ) 6.5 Hz, 3H), 2.10-
2.75 (m, 4H), 2.88 (dt, J ) 3.5, 6.5 Hz, 1H), 3.88 (m, 1H), 4.14
(m, 1H), 4.43 (m, 1H), 5.26-5.68 (m, 2H); 13C NMR δ 18.2,
37.1, 39.1, 40.2, 66.1, 81.9, 125.2, 129.1; MS EI m/ z (rel inten)
252 (2), 197 (30), 125 (5), 70 (100), 55 (21). Anal. Calcd for
C8H13IO: C, 38.12; H, 5.20. Found: C, 38.42; H, 5.33.
(2R*,3R*)-3-Iod o-2-(3-m eth yl-2-bu ten yl)tetr a h yd r ofu -
r a n (18): 1H NMR (200 MHz, CDCl3) δ 1.67 (s, 3H), 1.71 (d, J
) 0.5 Hz, 3H), 2.10-2.28 (m, 1H), 2.40-2.80 (m, 3H), 2.91 (dt,
J ) 4.0, 6.3 Hz, 1H), 3.94 (dt, J ) 4.0, 8.5 Hz, 1H), 4.18 (q, J
) 8.5 Hz, 1H), 4.49 (m, 1H), 5.10 (m, 1H); 13C NMR δ 18.4,
25.8, 34.1, 36.3, 39.0, 66.1, 82.1, 118.8, 134.6; MS EI m/ z (rel
inten) 266 (4), 197 (48), 139 (5), 70 (91), 69 (100), 41 (50). Anal.
Calcd for C9H15IO: C, 40.62; H, 5.68. Found: C, 40.51; H,
5.79.
(3Z)-7-Meth yl-3,6-octa d ien -1-ol (10c): 1H NMR (200 MHz,
CDCl3) δ 1.38 (t, J ) 6.5 Hz, 1H (OH)), 1.67 (s, 3H), 1.73 (d, J
) 0.5 Hz, 3H), 2.38 (q, J ) 6.5 Hz, 2H), 2.78 (t, J ) 6.5 Hz,
2H), 3.68 (q, J ) 6.5 Hz, 2H), 5.10 (tq, J ) 0.5, 6.5 Hz, 1H),
5.30-5.65 (m, 2H); MS EI m/ z (rel inten) 140 (7), 122 (5), 107
(36), 97 (14), 95 (11), 93 (18), 91 (25), 83 (14), 81 (13), 79 (39),
77 (22), 69 (34), 67 (100), 55 (66), 53 (36), 41 (66). Anal. Calcd
for C9H16O: C, 77.09; H, 11.50. Found: C, 76.91; H, 11.70.
(3Z)-6-Meth yl-3,6-h ep ta d ien -1-ol (10d ): 1H NMR (200
MHz, CDCl3) δ 1.43 (s, 1H), 1.74 (s, 3H), 2.36 (q, J ) 6.5 Hz,
2H), 2.79 (d, J ) 6.5 Hz, 2H), 3.66 (t, J ) 6.5 Hz, 2H), 4.73
(m, 2H), 5.43-5.72 (m, 2H); MS EI m/ z (rel inten) 126 (6),
111 (17), 108 (4), 95 (51), 93 (80), 91 (36), 83 (11), 82 (38), 81
(35), 80 (28), 79 (60), 77 (48), 67 (100), 55 (65), 53 (46), 41 (61).
Anal. Calcd for C8H14O: C, 76.14; H, 11.18. Found: C, 76.01;
H, 11.38.
(3Z,6Z)-3,6-Octadien -1-ol (10f): 1H NMR (200 MHz, CDCl3)
δ 1.58 (s, 1H), 1.64 (d, J ) 6 Hz, 3H), 2.49 (q, J ) 6.5 Hz, 2H),
2.85 (t, J ) 6.5 Hz, 2H), 3.66 (t, J ) 6.5 Hz, 2H), 5.28-5.67
(m, 4H); MS EI m/ z (rel inten) 126 (0.5), 108 (5), 95 (15), 93
(88), 91 (40), 82 (25), 81 (25), 79 (64), 77 (51), 67 (100), 65 (20),
55 (47), 53 (26), 41 (22). Anal. Calcd for C8H14O: C, 76.14;
H, 11.18. Found: C, 76.29; H, 11.36.
(3Z)-6-Meth oxy-3,6-h ep ta d ien -1-ol (10e). A suspension
of 25 mg of Pd over BaSO4 in 10 mL of hexane was stirred
under H2 for 30 min at rt. Then 4 µL of quinoline and 200 mg
(1.4 mmol) of alcohol 9e were added, and the mixture was
stirred until 1 equiv of H2 was absorbed. After filtration on a
Bu¨chner funnel, the filtrate was concentrated under vacuum,
and the sensitive alcohol 10e was used without further
purification for the iodoetherification: 1H NMR (250 MHz,
CDCl3) δ 1.77 (m, 1H), 2.38 (q, J ) 6.5 Hz, 2H), 2.90 (d, J )
7.5 Hz, 2H), 3.54 (s, 3H), 3.62-3.71 (m, 2H), 3.91 (d, J ) 2
Hz, 1H), 4.34 (d, J ) 2 Hz, 1H), 5.46-5.72 (m, 2H).
2-(1-Iod o-4-m eth yl-3-p en ten yl)oxeta n e (19): 1H NMR
(200 MHz, CDCl3) δ 1.67 (s, 3H), 1.74 (d, J ) 0.5 Hz, 3H),
2.16-2.63 (m, 4H), 3.75-4.00 (m, 3H), 4.09 (dt, J ) 1.0, 6.3
Hz, 1H), 5.18 (m, 1H); 13C NMR δ 18.1, 23.1, 26.0, 31.2, 38.5,
67.2, 88.3, 119.2, 134.9; MS EI m/ z (rel inten) 266 (3), 197
(70), 139 (5), 69 (100), 57 (10), 41 (52). Anal. Calcd for C9H15
-
IO: C, 40.62; H, 5.68. Found: C, 40.63; H, 5.82.
1
2-(Iod om eth yl)-2-m eth yl-4-oxep en e (20): H NMR (200
MHz, CDCl3) δ 1.36 (s, 3H), 2.38 (m, 2H), 2.57 (dq, J ) 6.0,
15.0 Hz, 2H), 3.45 (AB pattern, ∆ν ) 8.5 Hz, J ) 10 Hz, 2H),
3.84 (t, J ) 6 Hz, 2H), 5.53-5.68 (m, 1H), 5.72-5.85 (m, 1H);
13C NMR δ 17.6, 26.4, 32.9, 36.2, 62.3, 76.5, 125.3, 131.0; MS
EI m/ z (rel inten) 252 (1), 125 (25), 111 (4), 68 (100), 67 (38),
53 (20). Anal. Calcd for C8H13IO: C, 38.12; H, 5.20. Found:
C, 38.30; H, 5.28.
2-(Iod om eth yl)-4-oxep en en e (11): 1H NMR (250 MHz,
CDCl3) δ 2.15-2.59 (m, 4H), 3.25 (d, J ) 6 Hz, 2H), 3.40-
3.56 (m, 2H), 4.11 (ddd, J ) 4.0, 4.0, 12.5 Hz, 1H), 5.68-5.90
(m, 2H); 13C NMR δ 10.7, 32.0, 36.6, 69.7, 79.2, 127.9, 131.1;
MS EI m/ z (rel inten) 238 (8), 111 (24), 97 (12), 79(21), 68
(80), 67 (100), 55 (31), 43 (41). Anal. Calcd for C7H11IO: C,
35.32; H, 4.66. Found: C, 35.43; H, 4.71.
(2R*,3R*)-3-Iod o-2-(2-p r op en yl)tetr a h yd r ofu r a n (12):
1H NMR (200 MHz, CDCl3) δ 1.05-1.80 (m, 2H), 2.22-3.06
(m, 2H), 3.85-3.99 (m, 2H), 4.04-4.22 (m, 1H), 4.45-4.50 (m,
1H), 5.08-5.30 (m, 2H), 5.82 (ddt, J ) 6.5, 10.5, 17.0 Hz, 1H);
13C NMR δ 14.1, 31.8, 39.0, 65.8, 80.8, 124.3, 133.5; MS EI
m/ z (rel inten) 238 (6), 197 (19), 168 (13), 111 (100), 71 (83),
70 (88), 69 (21), 55 (31). Anal. Calcd for C7H11IO: C, 35.32;
H, 4.66. Found: C, 35.51; H, 4.80.
2-(Iod om eth yl)-2-m eth oxy-4-oxep en e (21): 1H NMR (200
MHz, CDCl3) δ 2.16-2.90 (m, 4H), 3.24 (s, 3H), 3.36 (s, 2H),
3.76 (dt, J ) 3.5, 12.5 Hz, 1H), 4.15 (ddd, J ) 3.5, 11.8, 12.5
Hz, 1H), 5.43-5.74 (m, 2H); 13C NMR δ 9.2, 32.5, 34.0, 47.8,
62.0, 102.9, 122.6, 130.5. Anal. Calcd for C8H13IO2: C, 35.84;
H, 4.89. Found: C, 35.65; H, 4.70.
7-Octen -1-ol (22a ).44 This alcohol was obtained by LiAlH4
reduction in ether of 7-octenoic acid.45
3,3-Dim eth yl-7-octen -1-ol (22b). This alcohol was ob-
tained by LiAlH4 reduction in ether of ethyl 3,3-dimethyl-7-
octenoate, prepared according to ref 46 by addition of 4-penten-
1-yl magnesium bromide to ethyl 3,3-dimethylacrylate in the
presence of Cu(I)Cl: 1H NMR (200 MHz, CDCl3) δ 0.89 (s, 6H),
1.06-1.45 (m, 4H), 1.48-1.58 (m, 3H), 2.05 (q, J ) 6.5 Hz,
2H), 3.62-3.74 (m, 2H), 4.92 (dd, J ) 2.0, 10.5 Hz, 1H), 5.00
(dd, J ) 2.0, 17.0 Hz, 1H), 5.81 (ddt, J ) 6.5, 10.5, 17.0 Hz,
1H).
7-Meth yl-7-octen -1-ol (22c). Prepared as reported in ref
36: 1H NMR (250 MHz, CDCl3) δ 0.80-1.60 (m, 9H), 1.70 (s,
3H), 2.01 (t, J ) 7.5 Hz, 2H), 3.65 (t, J ) 7.5 Hz, 2H), 4.70 (m,
2H).
7-Meth oxy-6-h ep ten -1-ol (22d ). The experimental pro-
tocol reported for the preparation compound 2h was used
(similar yields): Z/ E mixture 40/60; 1H NMR (200 MHz,
CDCl3) δ 1.21-1.70 (m, 7H), 1.95 (q, J ) 6.5 Hz, 12H (E
isomer)), 2.08 (q, J ) 6.5 Hz, 0.8 H (Z isomer)), 3.51 (s, 1.8H
(E isomer)), 3.59 (s, 1.2H (Z isomer)), 4.35 (q, J ) 6.5 Hz, 0.4H
(2R*,3S*)-3-Iod o-2-m eth yl-4-oxocen e (13): 1H NMR (250
MHz, CDCl3) δ 1.88 (d, J ) 7.8 Hz, 3H), 2.16-2.61 (m, 4H),
3.12 (m, 1H), 3.50 (td, J ) 1.0, 10.5 Hz, 1H), 4.06-4.15 (m,
1H), 4.26 (td, J ) 4.7, 8.0 Hz, 1H), 5.70-5.90 (m, 1H). A small
d (J ) 7.8 Hz) was detected at 1.94 for the (2R*,3R*)
diastereoisomer; 13C NMR δ 23.9, 32.0, 32.5, 34.8, 69.7, 84.0,
128.2, 130.9; MS EI m/ z (rel inten) 252 (5), 125 (66), 97 (15),
82 (17), 81 (11), 68 (100), 67 (93), 57 (31), 41 (23). Anal. Calcd
for C8H13IO: C, 38.12; H, 5.20. Found: C, 38.31; H, 5.33.
2-(1-Iodoeth yl)-4-oxepen e (14): 1H NMR (200 MHz, CDCl3)
δ 1.39 (d, J ) 6.0 Hz, 3H), 2.00-2.62 (m, 4H), 3.54-4.18 (m,
4H), 5.38-5.66 (m, 2H); 13C NMR δ 10.7, 30.2, 32.8, 44.6, 69.7,
79.3, 126.9, 131.8; MS EI m/ z (rel inten) 252 (2), 125 (9), 97
(54), 79 (21), 68 (80), 67 (100), 55 (31), 41 (29). Anal. Calcd
for C8H13IO: C, 38.12; H, 5.20. Found: C, 37.98; H, 5.43.
(2R*,3R*)-2-[2(E)-Bu ten yl]-3-iod otetr a h yd r ofu r a n (15):
1H NMR (250 MHz, CDCl3) δ 1.68 (dd, J ) 1.0, 6.3 Hz, 3H),
(44) Cope, A. C.; Hecht, J . K. J . Am. Chem. Soc. 1962, 84, 4872.
(45) Colonge, J .; Lasfargues, P. Bull. Soc. Chim. Fr. 1962, 177.
(46) Cahiez, G.; Alami, M. Tetrahedron Lett. 1990, 31, 7425.