Page 23 of 58
The Journal of Organic Chemistry
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obtained as an oil (0.40 g, 86 %): H NMR (300 MHz, CDCl ): δ 3.76 (s, 6H), 4.28 (dt, J = 5.8, 1.4 Hz,
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H), 5.12- 5.24 (m, 4H), 5.85-6.03 (m, 1H), 6.37 (t, J = 2.2 Hz, 1H), 6.43 (d, J = 2.2 Hz, 2H), 7.25-7.41
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(m, 5H) ppm; C{ H} NMR (75.5 MHz, CDCl ): δ 53.3, 55.3, 67.3, 98.8, 106.1, 117.1, 127.8, 127.9,
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28.4, 133.9, 136.6, 143.8, 155.1, 160.7 ppm; IR (ATR): 1702 cm ; MS (ESI) m/z (rel intensity): 328.2
+
+
(MH , 93); HRMS (ESI-TOF): calcd. for C H NO : 328.1541 [MH ]; found, 328.1558.
19 22 4
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N-Allyl-N-(3,5-dimethoxyphenyl)acetamide
(1da).
Prepared
from
N-(3,5-
dimethoxyphenyl)acetamide (0.28 g, 1.43 mmol), NaH (60% in mineral oil) (62.9 mg, 1.57 mmol) and
allyl chloride (0.14 mL, 1.72 mmol). The reaction mixture was stirred at room temperature for 3 h. After
work-up and purification by flash column chromatography (silica gel, hexane/AcOEt 5/5) 1da was
1
obtained as an oil (0.32 g, 97 %): H NMR (300 MHz, CDCl ): δ 1.80 (s, 3H), 3.67 (s, 6H), 4.26 (d, J =
3
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.2 Hz, 2H), 5.02- 5.20 (m, 2H), 5.87 (ddt, J = 16.8, 10.7, 6.2 Hz, 1H), 6.31 (d, J = 2.1 Hz, 2H), 6.42 (t,
1
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J = 2.1 Hz, 1H) ppm; C{ H} NMR (75.5 MHz, CDCl ): δ 22.5, 51.8, 55.4, 99.5, 106.4, 117.7, 133.3,
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144.7, 161.2, 169.9 ppm; IR (ATR): 1652 cm ; MS (EI) m/z (rel intensity): 235.1 (M , 84), 192.1 (100);
+
HRMS (CI-TOF): m/z calcd. for C H NO : 236.1287 [MH ]; found, 236.1294.
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18
3
(
1R,2S,5R)-2-Isoprpyl-5-methylcyclohexyl allyl(3,5-dimethoxyphenyl)carbamate (1ga). Prepared
from (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl (3,5-dimethoxyphenyl)carbamate (A, see below)
0.45 g, 1.36 mmol), NaH (60% in mineral oil) (59.6 mg, 1.49 mmol) and allyl chloride (0.13 mL, 1.63
(
mmol). The reaction mixture was stirred at room temperature for 4 h. After work-up and purification by
flash column chromatography (silica gel, hexane/AcOEt 9/1) 1ga was obtained as an oil (0.37 g, 72 %):
[α]D20 –36.9 (c 2.75, CH Cl ); H NMR (300 MHz, CDCl ): δ 0.73-0.93 (m, 10H), 0.93-1.14 (m, 2H),
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.22-1.38 (m, 1H), 1.39-1.57 (m, 1H), 1.58-1.71 (m, 2H), 1.86-1.99 (m, 1H), 2.05-2.16 (m, 1H), 3.76 (s,
H), 4.23 (d, J = 5.6 Hz, 2H), 4.62 (td, J = 10.8, 4.3 Hz, 1H), 5.11-5.22 (m, 2H), 5.84-6.00 (m, 1H),
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6.32 (t, J = 2.2 Hz, 1H), 6.42 (d, J = 2.2 Hz, 2H) ppm; C{ H} NMR (75.5 MHz, CDCl ): δ 16.3, 20.8,
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2.0, 23.4, 26.2, 31.4, 34.3, 41.2, 47.1, 53.1, 55.3, 75.8, 98.4, 104.9, 116.7, 134.2 , 144.2, 155.0, 160.6
-1
+
ppm; IR (ATR): 1700 cm ; MS (ESI) m/z (rel intensity): 376.2 (MH , 23), 238.1 (87); HRMS (ESI-
+
TOF): calcd. for C H NO : 376.2488 [MH ]; found, 376.2491.
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