The Journal of Organic Chemistry
Note
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95%) as a colorless oil. H NMR (300 MHz, CDCl3): δ 3.78 (dd, J =
ppm. EI-MS (m/z, relative intensity): 152 (M+, 28), 123 (32), 95
(100), 81 (10), 55 (31), 41 (18). IR (neat, ν/cm−1): 2964, 2878, 1746,
1461, 1381, 1314, 1181, 1031. HRMS (ESI): m/z calcd for C10H16O
(M+) 152.1201, found 152.1194.
10.5, 4.0 Hz, 1H), 1.82−1.62 (m, 2H), 1.57−1.42 (m, 2H), 1.30−1.22
(m, 1H), 1.19−1.09 (m, 2H), 1.07 (s, 3H), 0.96 (s, 3H), 0.82 ppm (d,
J = 7.5 Hz, 1H) ppm. 13C NMR (75 MHz, CDCl3): δ 78.1 (d), 50.7
(t), 48.6 (s), 46.6 (s), 43.4 (d), 30.0 (t), 28.2 (t), 20.4 (q), 19.5 (q),
8.1 (q) ppm. EI-MS (m/z, relative intensity): 154 (M+, 1), 139 (2),
121 (5), 107 (8), 95 (100), 81 (22), 69 (7), 55 (5), 41 (7). IR (neat,
ν/cm−1): 3431, 2924, 2856, 1623, 1532, 1457, 1378, 1351. HRMS
(ESI): m/z calcd for C10H18O (M+) 154.1358, found 154.1357.
1,3-endo-4-Trimethylbicyclo[2.2.1]heptan-2-yl 4-Nitrobenzoate
((endo)-15b″). An argon-flushed flask was charged with the alcohol
(endo)-15b′ (8.00 g, 52.0 mmol), triethylamine (10.6 g, 104 mmol),
N,N-dimethyl-4-aminopyridine (7.60 g, 62.0 mmol), and dichloro-
methane (100 mL) at 0 °C. 4-Nitrobenzoyl chloride (14.2 g, 78.0
mmol) was added. The reaction mixture was stirred at room
temperature for 12 h. Then water (50 mL) was added. The aqueous
layer was extracted with MTBE (50.0 mL), and the combined organic
phases were dried with MgSO4 and concentrated in vacuo. The residue
was purified by column chromatography (hexane/MTBE 100/1) to
yield the product (5.40 g, 34%) as a white solid. Mp: 69.5−70.5 °C. 1H
NMR (300 MHz, CDCl3): δ 8.61−7.97 (m, 4H), 5.16 (dd, J = 1.3,
10.4 Hz, 1H), 2.20−1.85 (m, 2H), 1.76−1.58 (m, 1H), 1.47−1.25 (m,
4H), 1.11 (s, 3H), 1.04 (s, 3H), 0.78 (d, J = 7.4 Hz, 3H) ppm. 13C
NMR (75 MHz, CDCl3): δ 164.8 (CO, s), 150.5 (s), 136.1 (s),
130.6 (d), 123.6 (d), 81.8 (d), 50.8 (t), 48.1 (s), 46.8 (s), 42.9 (d),
30.0 (t), 29.8 (t), 20.0 (q), 19.5 (q), 8.5 (q) ppm. EI-MS (m/z, relative
intensity): 303 (M+, 1), 273 (2), 260 (3), 150 (29), 136 (15), 121
(12), 107 (22), 95 (100), 81 (15), 67 (5), 55 (4), 41 (4). IR (neat, v/
cm−1): 3114, 3084, 2954, 2872, 1724, 1606, 1530, 1456, 1347, 1277,
1112, 1018, 976, 870, 839, 793, 719. HRMS (EI): m/z calcd for
C17H21NO4 (M+) 303.1471, found 303.1472.
7-Methyl-1-pentylbicyclo[2.2.1]heptan-2-one (15g). Colorless
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liquid; 0.35 g, 18% yield. H NMR (300 MHz, CDCl3): δ 2.24 (dd,
J = 2.1, 17.4 Hz, 2H), 1.98−1.77 (m, 4H), 1.52 (m, 2H), 1.45−1.20
(m, 8H), 0.91−0.81 (m, 6H, 2CH3) ppm. 13C NMR (75 MHz,
CDCl3): δ 219.8 (CO, s), 59.3 (s), 45.7 (d), 41.5 (t), 38.6 (d), 32.7
(t), 28.1 (t), 27.3 (t), 25.8 (t), 23.9 (t), 22.6 (t), 14.1 (q), 11.0 (q)
ppm. EI-MS (m/z, relative intensity): 194 (M+, 34), 150 (38), 109
(14), 95 (52), 81 (100), 67 (25), 55 (25), 41 (22). IR (neat, ν/cm−1):
2957, 2874, 1741, 1466, 1414, 1381, 1328, 1293, 1260, 1166, 1085,
1067. HRMS (ESI): m/z calcd for C13H22O (M+) 194.1671, found
194.1679.
1,2-trans-1-(2-Methylcyclohex-3-enyl)hexan-1-one (22). Color-
less liquid; 0.37 g, 19% yield. 1H NMR (300 MHz, CDCl3): δ
5.66−5.61 (m, 1H), 5.53−5.47 (m, 1H), 2.58−2.20 (m, 4H), 2.10−
2.04 (m, 2H), 1.90−1.80 (m, 1H), 1.65−1.50 (m, 3H), 1.38−1.18 (m,
4H), 0.91 (d, J = 7.2 Hz, 3H, CH3), 0.90 (t, J = 7.2 Hz, 3H, CH3)
ppm. 13C NMR (75 MHz, CDCl3): δ 214.5 (CO, s), 132.6 (d),
125.2 (d), 54.7 (d), 42.1 (t), 31.6 (d), 31.5 (t), 25.7 (t), 24.9 (t), 24.9
(t), 23.3 (t), 22.5 (t), 20.2 (q), 13.9 (q) ppm. EI-MS (m/z, relative
intensity): 194 (M+, 6), 179 (2), 123 (13), 99 (100), 71 (53), 55 (19),
43 (40). IR (neat, ν/cm−1): 3020, 2927, 2872, 1737, 1652, 1457, 1408,
1374, 1207, 684, 429. HRMS (ESI): m/z calcd for C13H22O (M+)
194.1671, found 194.1661.
3,4-Dimethyl-1-(2,3,3-trimethylcyclopent-1-enyl)bicyclo[2.2.1]-
heptan-2-one (15h). This compound was prepared by following the
procedure reported by Baldwin and Lusch.12 The crude product was
purified by column chromatography, followed by bulb-to-bulb
distillation, to yield 1.84 g (75%) of a colorless liquid. 1H NMR
(300 MHz, CDCl3): δ 2.30−2.10 (m, 2H), 1.96−1.85 (m, 2H), 1.72
(s, 2H), 1.64−1.55 (m, 3H), 1.47 (s, 3H), 1.40−1.33 (m, 1H), 1.15 (s,
3H), 0.97 (d, J = 7.8 Hz, 3H), 0.96 (s, 3H), 0.95 (s, 3H), 0.87−0.79
(m, 1H) ppm. 13C NMR (75 MHz, CDCl3): δ 218.4 (CO, s), 142.3
(s), 129.5 (s), 60.5 (s), 53.9 (d), 49.1 (t), 47.8 (s), 44.6 (s), 38.7 (t),
32.6 (t), 32.5 (t), 28.5 (t), 26.7 (q), 26.5 (q), 19.8 (q), 11.4 (q), 8.9
(q) ppm. EI-MS (m/z, relative intensity): 246 (M+, 21), 231 (36), 203
(42), 189 (100), 174 (27), 135 (15), 95 (19). IR (neat, ν/cm−1):
2954, 2870, 1745, 1458, 1373. HRMS (ESI): m/z calcd for C17H26O
(M+) 246.1984, found 246.1970.
3-endo-4-Dimethyl-1-pentylbicyclo[2.2.1]heptan-2-one (15c).
Colorless liquid; 1.87 g, 90% yield. H NMR (300 MHz, CDCl3): δ
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1.85 (q, J = 6.9 Hz, 1H), 1.74−1.60 (m, 2H), 1.59−1.48 (m, 2H),
1.45−1.35 (m, 2H), 1.36−1.21 (m, 8H), 1.18 (s, 3H), 0.96 (d, J = 6.9
Hz, 3H), 0.85 (t, J = 6.6 Hz, 3H) ppm. 13C NMR (75 MHz, CDCl3): δ
221.3 (CO, s), 59.3 (s), 54.2 (d), 47.4 (t), 44.9 (t), 32.7 (t), 32.5
(t), 29.0 (t), 28.8 (t), 25.6 (t), 22.5 (t), 19.7 (q), 14.0 (q), 8.7 (q)
ppm. GC/MS (EI): 208 (M+, 25), 179 (12), 151 (100), 125 (11), 109
(24), 94 (18), 81 (21). IR (neat, ν/cm−1): 2928, 2870, 1742, 1458,
1372, 1323, 1301, 1249, 1181, 1135. HRMS (ESI): m/z calcd for
C14H24O (M+) 208.1827, found 208.1828.
(8a)-endo-2-Methyloctahydro-1H-2,4a-methanonaphthalen-1-
one (15d). Colorless liquid; 1.51 g, 85% yield. H NMR (300 MHz,
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rac-(3aR,4R,7S,7aR,8S)-8-Methoxy-4-methylhexahydro-4,7-
methanobenzofuran-2(3H)-one (28a). This compound was prepared
by following the procedure reported by Baldwin and Lusch.12 The
crude product was purified by column chromatography to yield 1.57 g
CDCl3): δ 2.00−1.50 (m, 9H), 1.48−1.18 (m, 6H), 1.15 (s, 3H) ppm.
13C NMR (75 MHz, CDCl3): δ 220.3 (CO, s), 57.7 (d), 55.4 (s),
50.1 (t), 45.8 (s), 34.1 (t), 33.2 (t), 27.3 (t), 26.0 (t), 22.4 (t), 21.2 (t),
14.3 (q) ppm. EI-MS (m/z, relative intensity): 178 (M+, 56), 160 (8),
150 (15), 135 (23), 121 (11), 107 (100), 94 (68), 81 (36), 67 (19), 55
(11), 41 (18). IR (neat, ν/cm−1): 2924, 2866, 1738, 1447, 1356, 1308,
1263, 1186. HRMS (ESI): m/z calcd for C12H18O (M+) 178.1358,
found 178.1362.
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(82%) of a white solid. Mp: 69.5−70.5 °C. H NMR (300 MHz,
CDCl3): δ 4.53 (d, J = 7.2 Hz, 1H), 3.33 (s, 3H), 3.24 (s, 1H), 2.65−
2.32 (m, 4H), 1.86−1.66 (m, 2H), 1.31−1.16 (m, 2H), 1.13 (s, 3H)
ppm. 13C NMR (75 MHz, CDCl3): δ 177.5 (CO, s), 85.1 (d), 83.6
(d), 57.6 (q), 46.5 (s), 44.7 (d), 42.5 (d), 33.6 (t), 29.8 (t), 21.8 (t),
13.9 (q) ppm. EI-MS (m/z, relative intensity): 196 (M+, 15), 164
(86), 149 (9), 137 (26), 122 (28), 105 (77), 94 (96), 81 (100), 71
(90), 55 (39), 41 (58). IR (neat, ν/cm−1): 2957, 2926, 2871, 1779,
1469, 1420, 1362, 1297, 1193, 1127, 1113, 1031, 885, 539. HRMS
(ESI): m/z calcd for C11H16O3 (M+) 196.1099, found 196.1087.
rac-(3aR,4R,7S,7aR,8S)-8-Methoxy-4-pentylhexahydro-4,7-meth-
anobenzofuran-2(3H)-one (28b). This compound was prepared by
following the procedure reported by Baldwin and Lusch.12 The crude
product was purified by column chromatography to yield 2.24 g (89%)
1-Heptylbicyclo[2.2.1]heptan-2-one (15e). Colorless liquid; 1.04 g,
50% yield. H NMR (300 MHz, CDCl3): δ 2.55 (t, J = 3.9 Hz, 1H),
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2.15−2.05 (m, 1H), 1.92 (dd, J = 4.5, 17.7 Hz, 1H), 1.89−1.76 (m,
1H), 1.76−1.55 (m, 3H), 1.54−1.34 (m, 4H), 1.34−1.15 (m, 10H),
0.86 (t, J = 7.2 Hz, 3H) ppm. 13C NMR (75 MHz, CDCl3): δ 218.9
(CO, s), 57.9 (s), 46.2 (t), 41.2 (t), 34.0 (d), 31.8 (t), 30.3 (t), 29.8
(t), 29.2 (t), 28.7 (t), 28.4 (t), 25.9 (t), 22.6 (t), 14.1 (q) ppm. EI-MS
(m/z, relative intensity): 208 (M+, 4), 166 (40), 164 (44), 121 (13),
109 (57), 95 (20), 80 (100), 67 (37), 55 (22), 41 (22). IR (neat, ν/
cm−1): 2957, 2926, 2856, 1746, 1458, 1408, 1377, 1294, 1174, 438,
414. HRMS (ESI): m/z calcd for C14H24O (M+) 208.1827, found
208.1813.
6-Ethyl-1-methylbicyclo[2.2.1]heptan-2-one (15f). Colorless
liquid; 0.68 g, 45% yield. H NMR (300 MHz, CDCl3): δ 2.55 (d, J
= 4.8 Hz, 1H), 1.90 (dd, J = 5.4, 10.5 Hz, 1H), 1.88−1.76 (m, 1H),
1.60−1.32 (m, 7H), 0.94 (s, 3H), 0.91 (dd, J = 7.8, 9.9 Hz, 3H) ppm.
13C NMR (75 MHz, CDCl3): δ 220.9 (CO, s), 51.1 (d), 50.7 (s),
50.5 (s), 50.5 (d), 40.2 (t), 26.6 (t), 25.6 (t), 25.6 (t), 9.4 (q), 8.4 (q)
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of a white solid. Mp: 73.5−74.5 °C. H NMR (300 MHz, CDCl3): δ
4.52 (d, J = 7.5 Hz, 1H), 3.31 (s, 3H), 3.23 (s, 1H), 2.61−2.36 (m,
4H), 1.86−1.75 (m, 1H), 1.72−1.38 (m, 3H), 1.36−1.07 (m, 8H),
0.88 (t, J = 6.0 Hz, 3H) ppm. 13C NMR (75 MHz, CDCl3): δ 177.6
(CO, s), 85.7 (d), 83.5 (d), 57.5 (q), 50.2 (s), 42.2 (d), 41.9 (d),
32.5 (t), 30.8 (t), 29.4 (t), 28.8 (t), 24.9 (t), 22.4 (t), 21.6 (t), 13.9 (q)
ppm. EI-MS (m/z, relative intensity): 252 (M+, 35), 220 (38), 181
(34), 161 (94), 149 (50), 137 (65), 121 (38), 105 (35), 93 (55), 71
(100), 55 (34), 41 (58). IR (neat, ν/cm−1): 2926, 2871, 1778, 1469,
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dx.doi.org/10.1021/jo500942a | J. Org. Chem. XXXX, XXX, XXX−XXX