The Journal of Organic Chemistry
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128.2 (CH), 126.1 (CH), 45.1 (CH2), 30.0 (CH3), 29.7 (CH2).
Data are consistent with those previously reported.49
1-(4-(Trifluoromethyl)phenyl)ethan-1-one (2i) (Table 2, Entry 9).
Compound 2i was isolated as a colorless oil: yield 54 mg (29%,
method A); νmax (CHCl3)/cm−1 1580, 1312, 1265, 1174, 1137; δH
(400 MHz; CDCl3) 8.08 (2 H, d, J 8.2, ArH), 7.75 (2 H, d, J 8.2,
ArH), 2.66 (3 H, s, CH3); δC (100 MHz; CDCl3) 196.9 (C), 139.7
(C), 134.5 (t, JFC 33, C), 128.6 (CH), 125.6 (q, JFC 3.7, CH), 123.6
(d, JFC 272, C), 26.7 (CH3). Data are consistent with those
previously reported.60
Benzophenone (2j) (Table 2, Entry 10; Table 4, Entry 6).
Compound 2j was isolated as a colorless oil: yield 109 mg (55%,
method A); 164 mg (90%, method B); νmax (CHCl3)/cm−1 3065,
1658, 1600, 1448, 1319, 1280, 910; δH (400 MHz; CDCl3) 7.82 (4
H, dd, J 8.4, 1.7, ArH), 7.60 (2 H, tt, J 7.3, 1.7, ArH), 7.49 (4 H, app
br t, J 7.8, ArH); δC (100 MHz; CDCl3) 196.7 (C), 137.6 (C), 132.4
(CH), 130.0 (CH), 128.2 (CH). Data are consistent with those
previously reported.50
Fluorenone (2k) (Table 2, Entry 11; Table 4, Entry 7).
Compound 2k was isolated as a brght yellow solid: yield 152 mg
(80%, method A); 110 mg (61%, method B); mp 80−83 °C (lit.61
mp 80−82 °C); νmax (CHCl3)/cm−1 3070, 1715, 1612, 1454, 1327,
918; δH (400 MHz; CDCl3) 7.67 (2 H, dt, J 7.3, 1.3, CH), 7.53−
7.47 (4 H, m, CH), 7.30 (2 H, td, J 7.3, 1.3, CH); δC (100 MHz;
CDCl3) 193.9 (C), 144.4 (C), 134.6 (CH), 134.1 (C), 129.0 (CH),
124.3 (CH), 120.3 (CH). Data are consistent with those previously
reported.61,62
2,3-Dihydro-1H-inden-1-one (2l) (Table 2, Entry 12; Table 4,
Entry 8). Compound 2l was isolated as a pale yellow oil: yield 53 mg
(40%, method A); 53 mg (40%, method B); νmax (CHCl3)/cm−1
3011, 1711, 1611, 1473, 1280, 909; δH (400 MHz; CDCl3) 7.75 (1
H, app br d, J 7.7, ArH), 7.58 (1 H, td, J 7.2, 1.0, ArH), 7.47 (1 H,
dt, J 7.7, 1.0, ArH), 7.36 (1 H, td, J 7.2, 1.0, ArH), 3.14 (2 H, t, J
5.6, CH2), 2.69−2.66 (2 H, m, CH2); δC (100 MHz; CDCl3) 207.0
(C), 155.1 (C), 137.0 (C), 134.5 (CH), 127.2 (CH), 126.6 (CH),
123.6 (CH), 36.1 (CH2), 25.7 (CH2). Data are consistent with those
previously reported.63
(S)-Perillaldehyde (2m) (Table 2, Entry 13). Compound 2m was
isolated as a colorless oil: yield 42% by GC, method A; [α] = =
−73.5° (c 0.285, EtOH); νmax (CHCl3)/cm−1 3007, 1710, 1418,
1360, 1240, 1090; δH (400 MHz; CDCl3) 9.44 (1 H, s, CH), 6.84−
6.83 (1 H, m, CH), 4.79 (1 H, s, CH), 4.74 (1 H, s, CH), 2.55−2.42
(2 H, m, 2 × CH), 2.30−2.00 (3 H, m, 3 × CH), 2.00−1.85 (1 H,
m, CH), 1.77 (3 H, s, CH3), 1.55−1.40 (1 H, m, CH); δC (100
MHz; CDCl3) 193.9 (CH), 150.7 (CH), 148.3 (C), 141.2 (C),
109.6 (CH2), 40.7 (CH), 31.7 (CH2), 26.3 (CH2), 21.5 (CH2), 20.7
(CH3). Data are consistent with those previously reported.53,64
Cyclohex-2-en-1-one (2n) (Table 2, Entry 14). Compound 2n
was isolated as a colorless oil: yield 50% by GC, method A; νmax
(CHCl3)/cm−1 3011, 1670, 1389, 909; δH (400 MHz; CDCl3) 6.99
(1 H, td, J 10.1, 4.0, CH), 6.02 (1 H, td, J 10.1, 1.9, CH), 2.43 (2 H,
t, J 6.2, CH2), 2.37−2.33 (2 H, m, CH2), 2.02 (2 H, pent, J 6.2,
CH2); δC (100 MHz; CDCl3) 199.7 (C), 150.6 (CH), 129.9 (CH),
38.1 (CH2), 25.6 (CH2), 22.7 (CH2). Data are consistent with those
previously reported.65
3,5,5-Trimethylcyclohex-2-en-1-one (2o) (Table 2, Entry 15).
Compound 2o was isolated as a colorless oil: yield 75 mg (54%,
method A); νmax (CHCl3)/cm−1 2960, 1668, 1467, 1380, 1247, 1034;
δH (400 MHz; CDCl3) 5.91 (1 H, q, J 1.4, CH), 2.23 (2 H, s, CH2),
2.19 (2 H, s, CH2), 1.97 (3 H, s, CH3), 1.00 (6 H, s, CH3); δC (100
MHz; CDCl3) 200.0 (C), 160.4 (C), 125.5 (CH), 50.8 (CH2), 45.3
(CH2), 33.6 (C), 28.3 (CH3), 24.6 (CH3). Data are consistent with
those previously reported.66
4-Methoxybenzaldehyde (2b) (Table 2, Entry 2; Table 4, Entry
2). Compound 2b was obtained as a colorless oil: yield 75 mg (55%,
method A); 57 mg (42%, method B); νmax (CHCl3)/cm−1 3011,
1697, 1600, 1512, 1315, 1239, 1029; δH (400 MHz; CDCl3) 9.90 (1
H, s, CH), 7.86 (2 H, d, J 8.8, ArH), 7.02 (2 H, d, J 8.8, ArH), 3.91
(3 H, s, CH3); δC (100 MHz; CDCl3) 190.8 (CH), 164.6 (C), 132.0
(CH), 130.0 (C), 114.3 (CH), 55.6 (CH3). Data are consistent with
those previously reported.50 In addition, 4-methoxybenzoic acid 3
was isolated as a colorless solid: yield 25 mg, (16%, method B); mp
178−179 °C (lit.51 mp 182−183 °C); νmax (CHCl3)/cm−1 3051,
1686, 1605, 1259, 1182; δH (400 MHz; MeOD) 7.99 (2 H, d, J 8.9,
ArH), 6.99 (2 H, d, J 8.9, ArH), 3.87 (3 H, s, CH3); δC (100 MHz;
MeOD) 169.9 (C), 165.2 (C), 133.0 (CH), 124.1 (C), 114.8 (CH),
56.1 (CH3). Data are consistent with those previously reported.52
4-Methylbenzaldehyde (2c) (Table 2, Entry 3). Compound 2c
was isolated as a colorless oil: yield 23 mg (19%, method A); νmax
(CHCl3)/cm−1 3011, 2740, 1703, 1688, 1606, 1169, 909; δH (400
MHz; CDCl3) 9.97 (1 H, s, CH), 7.78 (2 H, d, J 8.2, ArH), 7.34 (2
H, d, J 8.2, ArH), 2.45 (3 H, s, CH3); δC (100 MHz; CDCl3) 192.0
(CH), 145.5 (C), 134.2 (C), 129.8 (CH), 129.7 (CH), 21.8 (CH3).
Data are consistent with those previously reported.53
4-Chlorobenzaldehyde (2d) (Table 2, Entry 4; Table 4, Entry 3).
Compound 2d was isolated as a pale yellow oil: yield 51 mg (36%,
method A); 21 mg (15%, method B, using 20 mol % BQH2 and 1.4
mol % 4); νmax (CHCl3)/cm−1 1736, 1596, 1422, 1239, 1094, 836;
δH (400 MHz; CDCl3) 9.99 (1 H, s, CH), 7.84 (2 H, d, J 8.5, ArH),
7.53 (2 H, d, J 8.5, ArH); δC (100 MHz; CDCl3) 190.8 (CH), 141.0
(C), 134.7 (C), 130.9 (CH), 129.5 (CH). Data are consistent with
those previously reported.50 In addition, 4-chlorobenzoic acid was
isolated as a colorless solid: yield 88 mg, (56%, method B); mp
238−241 °C (lit.54 mp 238−239 °C); νmax (CHCl3)/cm−1 3633,
3468, 3010, 2681, 1698, 1117; δH (400 MHz; MeOD) 8.01 (2 H, d,
J 8.5, ArH), 7.49 (2 H, d, J 8.5, ArH); δC (100 MHz; MeOD) 168.9
(C), 140.4 (C), 132.5 (CH), 130.9 (C), 129.9 (CH). Data are
consistent with those previously reported.52
4-(Trifluoromethyl)benzaldehyde (2e) (Table 2, Entry 5).
Compound 2e was isolated as a pale yellow oil: yield 43 mg
(25%; method A); νmax (CHCl3)/cm−1 2837, 1710, 1325, 1175,
1138, 1106, 836; δH (400 MHz; CDCl3) 10.11 (1 H, s, CH), 8.01 (2
H, d, J 8.3, ArH), 7.81 (2 H, d, J 8.3, ArH); δC (100 MHz; CDCl3)
191.0 (CH), 138.7 (C), 135.6 (C, d, JFC 32), 129.9 (CH), 126.1
(CH, q, JFC 3.8), 123.4 (C, d, JFC 273). Data are consistent with
those previously reported.55
1-(4-Methoxyphenyl)ethan-1-one (2f) (Table 2, Entry 6; Table 4,
Entry 4). Compound 2f was isolated as a pale yellow solid: yield 65
mg (43%, method A); 55 mg (37%, method B); mp 31−33 °C (lit.56
mp 30−31 °C); νmax (CHCl3)/cm−1 2964, 1614, 1589, 1508, 1466,
1288, 1180, 1037; δH (400 MHz; CDCl3) 7.94 (2 H, d, J 9.0, ArH),
6.94 (2 H, d, J 9.0, ArH), 3.87 (3 H, s, CH3), 2.56 (3 H, s, CH3); δC
(100 MHz; CDCl3) 196.8 (C), 163.5 (C), 130.6 (CH), 130.3 (C),
113.7 (CH), 55.4 (CH3), 26.3 (CH3). Data are consistent with those
previously reported.56,57
1-(4-Tolyl)ethan-1-one (2g) (Table 2, Entry 7). Compound 2g
was isolated as a pale yellow oil: yield 65 mg (48%, method A); νmax
(CHCl3)/cm−1 3011, 1678, 1574, 1270; δH (400 MHz; CDCl3) 7.88
(2 H, d, J 8.1, ArH), 7.28 (2 H, d, J 8.1, ArH), 2.60 (3 H, s, Me),
2.43 (3 H, s, Me); δC (100 MHz; CDCl3) 197.8 (C), 143.9 (C),
134.7 (C), 129.2 (CH), 128.4 (CH), 26.5 (CH3), 21.6 (CH3). Data
are consistent with those previously reported.58
1-(4-Chlorophenyl)ethan-1-one (2h) (Table 2, Entry 8; Table 4,
Entry 5). Compound 2h was isolated as a pale yellow oil: yield 75
mg (49%, method A, using 2 equiv of BQ); 109 mg (70%, method
B); νmax (CHCl3)/cm−1 1684, 1591, 1359, 1262, 1096, 833; δH (400
MHz; CDCl3) 7.90 (2 H, d, J 8.6, ArH), 7.44 (2 H, d, J 8.6, ArH),
2.59 (3 H, s, Me); δC (100 MHz; CDCl3) 196.8 (C), 139.6 (C),
135.4 (C), 129.7 (CH), 128.9 (CH), 26.5 (CH3). Data are
consistent with those previously reported.59
4-tert-Butylcyclohexan-1-one (2p) (Table 2, Entry 16; Table 4,
Entry 9). Compound 2p was isolated as a colorless solid: yield 54 mg
(35%, method A), 50 mg (32%, method B, cocatalyst added in 2
portions at 0 and 3 h); mp 44−46 °C (lit.67 mp 44−47 °C); νmax
(CHCl3)/cm−1 2963, 1711, 1368; δH (400 MHz; CDCl3) 2.43−2.29
(4 H, m, CH), 2.11−2.07 (2 H, m, CH), 1.55−1.43 (3 H, m, CH),
0.92 (9 H, s, CH3); δC (100 MHz; CDCl3) 212.6 (C), 46.7 (CH),
41.3 (CH2), 32.5 (C), 27.6 (CH2 and CH3). Data are consistent
with those previously reported.67−69
H
dx.doi.org/10.1021/jo5020917 | J. Org. Chem. XXXX, XXX, XXX−XXX