The Journal of Organic Chemistry
Note
orbitrap) m/z: [M + Na]+ calcd for C11H19NNaO, 204.1359; found,
204.1360.
gel (dichloromethane/methanol, 30:1). 1H NMR (400 MHz,
CDCl3): δ 7.34−7.38 (m, 2H), 7.26−7.32 (m, 2H), 7.19−7.26 (m,
1H), 6.30 (t, J = 3.8 Hz, 1H), 5.54 (br. d, J = 7.9 Hz, 1H), 5.06−5.12
(m, 1H), 2.18−2.26 (m, 2H), 1.85−1.96 (m, 2H), 1.83 (s, 3H),
1.68−1.78 (m, 1H), 1.54−1.66 (m, 1H). 13C{1H} NMR (100 MHz,
CDCl3): δ 169.4, 139.3, 136.6, 129.6, 128.5, 127.3, 125.6, 44.7, 29.8,
26.0, 23.5, 18.2. HRMS (ESI-Q-orbitrap) m/z: [M + Na]+ calcd for
C14H17NNaO, 238.1202; found, 238.1202.
2-(Cyclohex-1-en-1-yl)-N-(cyclohex-2-en-1-yl)acetamide (2m).
Yield: 95%, 62.5 mg. Purified by flash column chromatography
1
through silica gel (dichloromethane/methanol, 40:1). H NMR (500
MHz, CDCl3): δ 5.78−5.83 (m, 1H), 5.71 (br. d, J = 7.7 Hz, 1H),
5.55−5.59 (m, 1H), 5.48−5.53 (m, 1H), 4.39−4.46 (m, 1H), 2.81 (s,
2H), 1.89−2.04 (m, 6H), 1.81−1.88 (m, 1H), 1.49−1.63 (m, 6H),
1.40−1.49 (m, 1H). 13C{1H} NMR (125 MHz, CDCl3): δ 170.3,
133.0, 130.9, 127.8, 126.7, 46.5, 44.5, 29.5, 28.3, 25.4, 24.8, 22.8, 22.1,
19.8. HRMS (ESI-Q-orbitrap) m/z: [M + Na]+ calcd for
C14H21NNaO, 242.1515; found, 242.1515.
N-(4,4-Dimethylcyclohex-2-en-1-yl)acetamide (3d).11 Yield: 72%,
36.1 mg. Purified by flash column chromatography through silica gel
1
(dichloromethane/methanol, 40:1). H NMR (400 MHz, CDCl3): δ
5.55 (dd, J = 10.0, 1.7 Hz, 1H), 5.41 (dd, J = 10.0, 3.2 Hz, 2H), 4.36−
4.38 (m, 1H), 1.97 (s, 3H), 1.88−1.95 (m, 1H), 1.45−1.56 (m, 3H),
0.99 (s, 3 H), 0.97 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ
169.5, 141.3, 125.3, 45.1, 34.5, 31.8, 29.4, 29.3, 26.7, 23.7.
N-(Cyclohex-2-en-1-yl)acrylamide (2n). Yield: 98%, 44.5 mg.
Purified by flash column chromatography through silica gel
1
(dichloromethane/methanol, 40:1). H NMR (500 MHz, CDCl3):
δ 6.23 (dd, J = 17.0, 1.6 Hz, 1H), 6.11 (dd, J = 16.8, 10.1 Hz, 2H),
5.79−5.84 (m, 1H), 5.57 (dd, J = 10.1, 1.7 Hz, 1H), 5.53−5.58 (m,
1H), 4.47−4.55 (m, 1H), 1.93−2.00 (m, 2H), 1.84−1.92 (m, 1H),
1.57−1.68 (m, 2H), 1.47−1.57 (m, 1H). 13C{1H} NMR (125 MHz,
CDCl3): δ 164.9, 131.2, 130.9, 127.6, 126.1, 44.8, 29.4, 24.8, 19.8.
HRMS (ESI-Q-orbitrap) m/z: [M + Na]+ calcd for C7H13NNaO,
174.0889; found, 174.0890.
N-(6,6-Dimethylcyclohex-2-en-1-yl)acetamide (3d′). Yield: 17%,
8.5 mg. Purified by flash column chromatography through silica gel
1
(dichloromethane/methanol, 40:1). H NMR (400 MHz, CDCl3): δ
5.71−5.77 (m, 1H), 5.37−5.44 (m, 2H), 4.25−4.32 (m, 1H), 1.97−
2.04 (m, 5H), 1.34−1.48 (m, 2H), 0.94 (s, 3H), 0.85 (s, 3H).
13C{1H} NMR (100 MHz, CDCl3): δ 169.8, 129.2, 127.7, 52.8, 33.8,
32.9, 26.9, 23.7, 22.8, 22.5. HRMS (ESI-Q-orbitrap) m/z: [M + Na]+
calcd for C10H17NNaO, 190.1202; found, 190.1203.
N-(Cyclohex-2-en-1-yl)-2-cyclopropylacetamide (2o). Yield: 97%,
52.2 mg. Purified by flash column chromatography through silica gel
N-(2-Bromocyclohex-2-en-1-yl)acetamide (3e). Yield: 95%, 62.2
mg. Purified by flash column chromatography through silica gel
1
(dichloromethane/methanol, 40:1). H NMR (500 MHz, CDCl3): δ
1
6.05 (br. s, 1H), 5.75−5.79 (m, 1H), 5.49−5.53 (m, 1H), 4.39−4.45
(m, 1H), 2.06 (d, J = 7.2 Hz, 2H), 1.90−1.96 (m, 2H), 1.80−1.86 (m,
1H), 1.55−1.60 (m, 2H), 1.42−1.48 (m, 1H), 0.86−0.94 (m, 1H),
0.49−0.53 (m, 2H). 13C{1H} NMR (125 MHz, CDCl3): δ 171.7,
130.7, 127.9, 44.4, 41.5, 29.4, 24.8, 19.8, 7.2, 4.5. HRMS (ESI-Q-
orbitrap) m/z: [M + Na]+ calcd for C11H17NNaO, 202.1208; found,
202.1215.
(dichloromethane/methanol, 30:1). H NMR (400 MHz, CDCl3): δ
6.27 (br. d, J = 7.7 Hz, 1H), 6.20 (t, J = 4.0 Hz), 4.55−4.62 (m, 1H),
2.00−2.08 (m, 2H), 1.98 (s, 3H), 1.83−1.92 (m, 1H), 1.73−1.82 (m,
1H), 1.50−1.68 (m, 2H). 13C{1H} NMR (100 MHz, CDCl3): δ
169.8, 133.8, 122.4, 50.6, 30.9, 27.6, 23.3, 18.0. HRMS (ESI-Q-
orbitrap) m/z: [M + Na]+ calcd for C8H12BrNNaO, 239.9995; found,
239.9995.
N-(cyclohex-2-en-1-yl)benzamide (2p). Yield: 35%, 21.1 mg.
Purified by flash column chromatography through silica gel
Methyl 6-Acetamidocyclohex-1-enecarboxylate (3f). Yield: 96%,
56.8 mg. Purified by flash column chromatography through silica gel
1
1
(dichloromethane/methanol, 40:1). H NMR (400 MHz, CDCl3):
(dichloromethane/methanol, 20:1). H NMR (400 MHz, CDCl3): δ
δ 7.75−7.79 (m, 2H), 7.47−7.51 (m, 1H), 7.40−7.45 (m, 2H), 6.10
(br. s, 1H), 5.89−5.95 (m, 1H), 5.66−5.72 (m, 1H), 4.68−4.74 (m,
1H), 1.98−2.10 (m, 3H), 1.62−1.75 (m, 3H). 13C{1H} NMR (100
MHz, CDCl3): δ 166.8, 135.0, 131.5, 128.7, 127.7, 127.0, 45.2, 29.6,
25.0, 19.9. HRMS (APCI-Q-orbitrap) m/z: [M + Na]+ calcd for
C13H15NO, 202.1225; found, 202.1226.
N-(cyclohex-2-en-1-yl)-2-methylbenzamide (2q). Yield: 67%,
43.3 mg. Purified by flash column chromatography through silica
gel (dichloromethane/methanol, 30:1). 1H NMR (400 MHz,
CDCl3): δ 7.75−7.79 (m, 2H), 7.47−7.51 (m, 1H), 7.40−7.45 (m,
2H), 6.10 (br. s, 1H), 5.89−5.95 (m, 1H), 5.66−5.72 (m, 1H), 4.68−
4.74 (m, 1H), 1.98−2.10 (m, 3H), 1.62−1.75 (m, 3H). 13C{1H}
NMR (100 MHz, CDCl3): δ 166.8, 135.0, 131.5, 128.7, 127.7, 127.0,
45.2, 29.6, 25.0, 19.9. HRMS (APCI-Q-orbitrap) m/z: [M + Na]+
calcd for C13H15NO, 238.1202; found, 238.1209.
7.09 (t, J = 3.7 Hz, 1H), 5.90 (d, J = 7.4 Hz, 1H), 4.79−4.84 (m, 1H),
4.02−4.18 (m, 2H), 2.17−2.28 (m, 1H), 2.03−2.15 (m, 1H), 1.84−
1.92 (m, 4H), 1.59−1.67 (m, 1H), 1.43−1.57 (m, 2H), 1.19 (t, J =
7.2, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 169.0, 166.2, 144.1,
130.3, 60.5, 42.4, 28.5, 25.7, 23.3, 16.8, 14.2. HRMS (ESI-Q-orbitrap)
m/z: [M + Na]+ calcd for C10H15NNaO3, 220.0944; found, 220.0940.
N-(Cyclohept-2-en-1-yl)acetamide (3g). Yield: 66%, 30.3 mg.
Purified by flash column chromatography through silica gel
1
(dichloromethane/methanol, 30:1). H NMR (400 MHz, CDCl3):
δ 5.90 (br. s, 1H), 5.73−5.81 (m, 1H), 5.46−5.52 (m, 1H), 4.52−
4.60 (m, 1H), 2.03−2.20 (m, 2H), 1.95 (s, 3H), 1.75−1.90 (m, 2H),
1.59−1.72 (m, 2H), 1.45−1.56 (m, 1H), 1.28−1.39 (m, 1H).
13C{1H} NMR (100 MHz, CDCl3): δ 169.1, 134.9, 132.3, 50.6, 34.1,
28.6, 27.8, 26.8, 23.5. HRMS (ESI-Q-orbitrap) m/z: [M + Na]+ calcd
for C9H15NNaO, 176.10460; found, 176.1045.
N-(cyclohex-2-en-1-yl)-4-(trifluoromethoxy)benzamide (2r).
Yield: 90%, 77.0 mg. Purified by flash column chromatography
(Z)-N-(Cyclooct-2-en-1-yl)acetamide (3h). Yield: 87%, 43.7 mg.
Purified by flash column chromatography through silica gel
1
1
through silica gel (dichloromethane/methanol, 30:1). H NMR (400
(dichloromethane/methanol, 40:1). H NMR (400 MHz, CDCl3):
MHz, CDCl3): δ 7.32−7.35 (m, 1H), 7.27−7.31 (m, 1H), 7.16−7.21
(m, 2H), 5.87−5.91 (m, 1H), 5.76 (br. d, J = 6.2 Hz, 1H), 4.64−4.70
(m, 1H), 2.44 (s, 3H), 1.97−2.06 (m, 3H), 1.61−1.73 (m, 3H).
13C{1H} NMR (100 MHz, CDCl3): δ 169.5, 136.8, 135.9, 131.4,
131.0, 129.8, 127.5, 126.8, 125.8, 45.0, 29.6, 24.9, 19.8. HRMS (ESI-
Q-orbitrap) m/z: [M + Na]+ calcd for C14H17NNaO, 238.1202;
found, 238.1209.
δ 6.05 (t, J = 7.9 Hz, 1H), 5.88 (t, J = 7.9 Hz, 1H), 5.47−5.68 (m,
1H), 5.35 (br. d, J = 7.6 Hz, 1H), 3.68 (q, J = 9.9 Hz, 1H), 2.24−2.35
(m, 2H), 2.06−2.22 (m, 1H), 1.68−1.93 (m, 5H), 1.54−1.68 (m,
5H), 1.30−1.54 (m, 8H), 1.14−1.29 (m, 3H). 13C{1H} NMR (100
MHz, CDCl3): δ 169.3, 131.6, 130.2, 47.8, 36.6, 29.0, 26.5, 26.1, 24.4,
23.6. HRMS (ESI-Q-orbitrap) m/z: [M + Na]+ calcd for
C10H17NNaO, 190.1202; found, 190.1202.
N-(2-Methylcyclohex-2-en-1-yl)acetamide (3b). Yield: 95%, 43.7
mg. Purified by flash column chromatography through silica gel
N-(3-Methylbut-2-en-1-yl)acetamide (3i). Yield: 90%, 34.3 mg.
Purified by flash column chromatography through silica gel
1
1
(dichloromethane/methanol, 30:1). H NMR (400 MHz, CDCl3): δ
(dichloromethane/methanol, 30:1). H NMR (400 MHz, CDCl3):
5.80 (br. d, J = 7.25 Hz, 1H), 5.50−5.54 (m, 1H), 4.27−4.33 (m,
1H), 1.88−1.96 (m, 5H), 1.51−1.73 (m, 6H), 1.40−1.50 (m, 1H).
13C{1H} NMR (100 MHz, CDCl3): δ 169.7, 133.2, 126.1, 47.5, 29.8,
25.1, 23.4, 21.0, 18.7. HRMS (ESI-Q-orbitrap) m/z: [M + Na]+ calcd
for C9H15NNaO, 176.1046; found, 176.1046.
δ 6.00 (br. s, 1H), 5.10−5.16 (m, 1H), 3.75 (t, J = 6.2 Hz, 2H), 1.91
(s, 3H), 1.65 (s, 3H), 1.60 (s, 3H). 13C{1H} NMR (100 MHz,
CDCl3): δ 170.1, 136.1, 120.2, 37.6, 25.6, 23.1, 17.8. HRMS (ESI-Q-
orbitrap) m/z: [M + Na]+ calcd for C7H13NNaO, 150.0889; found,
150.0889.
N-(2,3,4,5-tetrahydro-[1,1′-biphenyl]-2-yl)acetamide (3c). Yield:
General Procedure for the Silver Salt Mediated Allylation
Reactions. 3-Bromocyclohexene (1a) (0.3 mmol, 1 equiv) was
63%, 40.7 mg. Purified by flash column chromatography through silica
6979
J. Org. Chem. 2021, 86, 6974−6982