Page 7 of 11
The Journal of Organic Chemistry
13C{1H} NMR (CDCl3, 75 MHz): δ 165.2, 144.6, 133.9, 130.5,
Yield 92% (103 mg); Clear liquid; 1H NMR (CDCl3, 500 MHz): δ
1
2
3
4
5
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7
8
127.5, 125.7, 124.4, 72.5, 31.7, 16.7.
9.82 (s, 1H), δ 7.67 (dd, 2H, J = 13.1, 4.0 Hz), 7.12 – 7.07 (m, 1H);
13C{1H} NMR (CDCl3, 125 MHz,): δ 182.8, 143.6, 136.4, 134.9,
128.2.
7-methoxyisochroman-1-one (2d)15b
:
Yield 87% (310 mg); Clear liquid; 1H NMR (CDCl3, 500 MHz): δ
7.59 (d, 1H, J = 2.6 Hz), 7.17 (d, 1H, J = 8.4 Hz), 7.10 (dd, 1H, J
= 8.4, 2.7 Hz), 4.52 (t, 2H, J = 6.0 Hz), 3.85 (s, 3H), 2.99 (t, 3H, J
= 6.0 Hz); 13C{1H} NMR (CDCl3, 125 MHz): δ 165.1, 158.8,
131.7, 128.2, 125.9, 121.5, 112.8, 67.5, 55.5, 26.8.
Pyridine-2-carboxyldehyde (4h)14l
:
1
Yield 72% (77 mg); Pale brown liquid; H NMR (CDCl3, 500
MHz): δ 9.93 (s, 1H), 8.65 (d, 1H, J = 4.6 Hz), 7.81 (d, 1H, J = 7.6
Hz), 7.75 (t, 1H, J = 7.6 Hz), 7.47 – 7.30 (m, 1H); 13C{1H} NMR
(CDCl3, 125 MHz): δ 193.3, 152.7, 150.1, 137.0, 127.9, 121.6.
Benzophenone (4j)40:
7-fluoroisochroman-1-one (2e)15b
:
Yield 67% (222 mg); White solid; 1H NMR (CDCl3, 300 MHz) δ
7.82 (d, 1H, J = 8.1 Hz), 7.42 – 7.17 (m, 2H), 4.59 (t, 2H, J = 6.0
Hz), 3.09 (t, 2H, J = 6.0 Hz); 13C{1H} NMR (CDCl3, 75 MHz): δ
164.2, 161.96 (d, J = 247.4 Hz), 135.41 (d, J = 3.3 Hz), 129.23 (d,
J = 7.4 Hz), 127.07 (d, J = 7.6 Hz), 121.22 (d, J = 22.2 Hz), 116.89
(d, J = 23.1 Hz), 67.6, 27.2; 19F NMR (CDCl3,, 282 MHz): δ -113.7
(dd, J = 14.6, 7.2 Hz).
Yield 95% (173 mg); White solid; 1H NMR (CDCl3, 500 MHz): δ
7.66 (d, 4H, J = 7.5 Hz), 7.51 (t, 2H, J = 7.2 Hz), 7.40 (t, 4H, J =
7.4 Hz); 13C{1H} NMR (CDCl3, 125 MHz): δ 195.0, 135.7, 130.9,
128.2, 126.7
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10
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12
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14
15
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24
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27
28
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32
33
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36
37
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39
40
41
42
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45
46
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48
49
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53
54
55
56
57
58
59
60
(4-chlorophenyl)(phenyl)methanone (4k)40:
Yield 91% (197 mg); White solid; 1H NMR (CD3OD, 500 MHz) δ
7.78 – 7.71 (m, 4H), 7.63 (t, 1H, J = 7.5 Hz), 7.55 – 7.48 (m, 4H);
13C{1H} NMR (CD3OD, 125 MHz): δ 197.1, 140.0, 138.4, 137.3,
133.9, 132.6, 130.9, 129.7, 129.6.
9H-xanthen-9-one (2f)15c
:
Yield 94% (368 mg); White solid; 1H NMR (CDCl3, 500 MHz): δ
8.35 (dd, 2H, J = 8.0, 1.6 Hz), 7.73 (m 2H), 7.51 (d, 2H, J = 8.4
Hz), 7.44 – 7.36 (m, 2H); 13C{1H} NMR (CDCl3, 125 MHz): δ
177.4, 156.3, 134.9, 126.9, 124.0, 122.0, 118.1.
phenyl(4-(trifluoromethyl)phenyl)methanone (4l)40:
Yield 92% (230 mg); White solid; 1H NMR (CD3OD, 500 MHz):
δ 7.91 (d, 2H, J = 8.1 Hz), 7.83 (d, 2H, J = 8.1 Hz), 7.80 – 7.75 (m,
2H), 7.65 (t, 1H, J = 7.5 Hz), 7.53 (t, 2H, J = 7.7 Hz); 13C{1H}
NMR (CD3OD, 125 MHz): δ 195.7, 140.9, 136.7, 133.3 (q, J =39
Hz), 133.0, 130.0, 129.7, 128.3, 125.1 (q, J = 3.7 Hz), 123.9 (q, J
= 324 Hz); 19F NMR (CD3OD, 282 MHz): δ -64.4
(3aR, 5aS, 9aS, 9bR)-3a,6,6,9a-tetramethyldecahydronaphtho[2,1-
b]furan2(1H)-one ((+)-Sclareolide) (2i)37:
Yield 48% (24 mg, 0.2 mmol scale); White solid; 1H NMR (CDCl3,,
500 MHz): δ 2.41 (dd, 1H, J = 16.1, 14.9 Hz), 2.24 (dd, 1H, J =
16.2, 6.5 Hz), 2.08 (dt, 1H, J = 11.9, 3.3 Hz), 1.97 (dd, 1H, J = 14.8,
6.5 Hz), 1.92 – 1.84 (m, 1H), 1.74 – 1.65 (m, 2H), 1.47 – 1.31 (m,
7H), 1.23 – 1.18 (m, 1H), 1.06 (dd, 2H, J = 12.7, 2.8 Hz), 0.91 (s,
3H), 0.88 (s, 3H), 0.84 (s, 3H); 13C{1H} NMR (CDCl3, 125 MHz):
δ 177.0, 86.5, 59.2, 56.7, 42.3, 39.6, 38.8, 36.1, 33.3, 33.2, 29.8,
28.8, 21.7, 21.0, 20.7, 18.2, 15.2; IR (neat, cm-1): 2920, 1761,
1157; [α]D28.0 = +46.7 (c = 1.00, CHCl3) (reported: [α]D28.7 = +46.9
(c = 1.00, CHCl3)37
Acetophenone (4m)18a
:
Yield 98% (118 mg); White solid; 1H NMR (CDCl3, 500 MHz): δ
7.79 (d, 2H, J = 7.6 Hz), 7.44 (t, 1H, J = 7.2 Hz), 7.33 (t, 2H, J =
7.5 Hz), 2.42 (s, 3H).
1-phenylprop-2-yn-1-one (4n)41:
Yield 86% (112 mg); White solid; 1H NMR (CDCl3, 500 MHz): δ
8.24 – 8.12 (m, 2H), 7.64 (t, 1H, J = 7.4 Hz), 7.51 (t, 2H, J = 7.8
Hz), 3.44 (s, 1H); 13C{1H} NMR (CDCl3, 125 MHz): δ 177.5,
136.2, 134.6, 129.8, 128.8, 80.8, 80.4.
Alcohol Oxidation products:
Benzaldehyde (4a)16l
:
1
Yield 95% (101 mg); Pale yellow liquid; H NMR (CDCl3, 500
MHz): δ 9.86 (s, 1H), 7.77 (d, 2H, J = 7.4 Hz), 7.56 (t, 1H, J = 7.1
Hz), 7.45 (t, 2H, J = 7.3 Hz); 13C{1H} NMR (CDCl3, 125 MHz): δ
191.4, 134.9, 133.0, 128.0, 127.5.
2-phenylacetaldehyde (4o)42:
Yield 80% (96 mg); Clear liquid; 1H NMR (CD2Cl2, 500 MHz): δ
9.72 (t, 1H, J = 2.0 Hz), 7.36 (t, 2H, J = 7.4 Hz), 7.29 (t, 1H, J =
7.4 Hz), 7.21 (d, 2H, J = 7.1 Hz), 3.68 (d, 1H, J = 2.0 Hz); 13C{1H}
NMR (CD2Cl2, 125 MHz): δ 200.1, 132.8, 130.1, 129.2, 127.6,
50.7.
4-hydroxybenzaldehyde (4b)38:
Yield 90% (110 mg); White solid; H NMR (CDCl3, 500 MHz) δ
1
9.86 (s, 1H), 7.82 (d, 2H, J = 7.2 Hz), 6.99 (d, 2H, J = 7.2 Hz), 6.48
(br, 1H); 13C{1H} NMR (CDCl3, 125 MHz): δ 191.5, 161.8, 132.7,
129.9, 116.1.
1-octanal (4p)18a
:
Yield 92% (118 mg); Clear liquid; 1H NMR (CDCl3, 500 MHz): δ
9.54 (m, 1H), δ 2.27 (t, 2H, J = 7.1 Hz), 1.49 – 1.41 (m, 2H), 1.21
– 1.07 (m, 8H), 0.73 (t, 3H, J = 6.4 Hz); 13C{1H} NMR (CDCl3,
125 MHz): δ 202.3, 42.2, 30.1, 27.5, 27.5, 21.0, 20.5, 12.2.
Terephthalaldehyde (4c)39:
Yield 91% (122 mg); White solid; 1H NMR (CDCl3, 500 MHz): δ
10.12 (s, 2H), 8.04 (s, 4H); 13C{1H} NMR (CDCl3, 125 MHz): δ
191.6, 140.1, 130.2
Cyclohexanone (4q)18a
:
1
Yield 94% (92 mg); Pale yellow liquid; H NMR (CDCl3, 500
MHz): δ 2.31 – 2.18 (m, 4H), 1.83 – 1.74 (m, 4H), 1.68 – 1.59 (m,
2H); 13C{1H} NMR (CDCl3, 125 MHz): δ 212.3, 41.8, 26.9, 24.9.
1-nitroso-2,4-dihydro-1H-benzo[d][1,3]oxazine (4s’):
4-nitrobenzaldehyde (4d)38:
Yield 75% (113 mg); Brown solid; 1H NMR (CDCl3, 500 MHz): δ
10.16 (s, 1H), 8.40 (d, 2H, J = 8.6 Hz), 8.08 (d, 2H, J = 8.6 Hz);
13C{1H} NMR (CDCl3, 125 MHz): δ 190.4, 151.2, 140.1, 130.6,
124.4.
1
Yield 81% (66 mg, 0.5 mmol scale); Pale yellow solid; H NMR
(CDCl3, 500 MHz): δ 8.05 (d, 1H, J = 8.2 Hz), 7.38 (t, 1H, J = 7.8
Hz), 7.28 (t, 1H, J = 7.5 Hz), 7.15 (d, 1H, J = 7.5 Hz), 5.43 (s, 2H),
4.86 (s, 2H); 13C{1H} NMR (CDCl3, 125 MHz): δ 135.0, 128.8,
126.5, 125.2, 122.7, 115.4, 73.7, 67.8; IR (neat, cm-1): 3071, 2971,
2867, 2853, 1458; HRMS (IT-TOF) m/z: [M+H]+ Calcd for
C8H9N2O2 165.0659; Found 165.0654
pyrene-1-carbaldehyde (4e)36d
:
Yield 98% (225 mg); Brown solid; 1H NMR (CDCl3, 500 MHz): δ
10.75 (s, 1H), 9.37 (d, 1H, J = 9.3 Hz), 8.40 (d, 1H, J = 7.9 Hz),
8.28 (dd, 3H, J = 8.1, 4.4 Hz), 8.20 (dd, 2H, J = 8.3, 6.4 Hz), 8.06
(dd, 2H, J = 14.0, 8.2 Hz); 13C{1H} NMR (CDCl3, 125 MHz): δ
193.1, 135.6, 131.4, 131.1, 131.0, 130.9, 130.8, 130.5, 127.4,
127.2, 127.1, 126.9, 126.6, 124.7, 124.6, 124.1, 123.0
Diol oxidation products:
dihydrofuran-2(3H)-one (6a)15e
:
Furan-2-carboxylaldehyde (4f)16f
:
Yield 88% (76 mg, 1 mmol scale); Clear liquid; 1H NMR (CDCl3,,
500 MHz): δ 4.27 (t, 2H, J = 7.1 Hz), 2.41 (t, 2H, J = 8.2 Hz), 2.30
– 2.11 (m, 2H); 13C{1H} NMR (CDCl3, 125 MHz): δ 177.8, 68.5,
27.7, 22.0.
1
Yield 91% (87 mg); Clear liquid; H NMR (CDCl3, 500 MHz): δ
9.62 (s, 1H), 7.73 – 7.61 (m, 1H), 7.26 – 7.18 (m, 1H), 6.57 (dd,
1H, J = 3.6, 1.7 Hz); 13C{1H} NMR (CDCl3, 125 MHz): δ 177.9,
153.0, 148.1, 121.2, 112.6.
1,4-dioxan-2-one (6b)15e
:
Thiophene-2-carboxyldehyde (4g)16l
:
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