Organometallics
Article
The resulting suspension was vigorously stirred at 80 °C for 0.5 h.
After completion of the reaction, the mixture was extracted with ethyl
acetate (3 × 10 mL). The combined ethyl acetate layer was then dried
over magnesium sulfate and concentrated in a vacuum. The resulting
crude product was purified by silica gel chromatography using a
mixture of 1/5 EtOA/petroleum ether as eluent to afford the
saturated alcohol product selectively.
General Procedure for Synthesis of Unsaturated Alcohols.
In a 10 mL Schlenk tube, formic acid (400 μL, 5 mmol) in four
batches was added to a stirred solution of α,β-unsaturated aldehydes 1
(1 mmol) and TC-6 catalyst (0.1 mol %) in deionized water (2 mL)
at 80 °C. The resulting suspension was stirred for 0.5 h. After
completion of the reaction, the mixture was extracted with ethyl
acetate (3 × 10 mL). The combined ethyl acetate layer was then dried
over magnesium sulfate and concentrated in a vacuum. The resulting
crude product was purified by silica gel chromatography using a
mixture of EtOAc/petroleum ether (1/5) as eluent to afford the
unsaturated alcohol product.
Procedure for Gram-Scale Selective Full Conduction of α,β-
Unsaturated Aldehyde. A mixture of (E)-2-methyl-3-phenyl-
acrylaldehyde 1i (10 mmol, 1.460 g), TC-6 catalyst (0.1 mol %,
5.50 mg), HCOONa (50 mmol, 3.400 g, 5.0 equiv), and 20 mL of
water was added to a 100 mL Schlenk tube, which was connected with
a condenser sealing and then vigorously stirred together at 80 °C for 4
h. After completion of the reaction, the mixture was extracted with
ethyl acetate (3 × 60 mL). The combined ethyl acetate layer was then
dried over sodium sulfate and concentrated in a vacuum. After
evaporation of the solvent, the crude mixture was purified by silica gel
column chromatography to afford 2i (1.380 g, >98% purity, 92%
yield, >99/1 2i/3i).
2-Methyl-3-phenyl-propan-1-ol (2i). Colorless oil. Yield: 145.6
mg, 97%. 1H NMR (400 MHz, CDCl3) δ 7.34−7.30 (m, 2H), 7.25−
7.20 (m, 3H), 3.52 (q, J = 10.6 Hz, 2H), 2.79 (d, J = 13.4 Hz, 1H),
2.44 (d, J = 13.4 Hz, 1H), 1.97 (s, 1H), 0.94 (s, 3H); 13C NMR (100
MHz, CDCl3) δ 140.7, 129.2, 128.3, 125.9, 67.6, 39.6, 16.4.
2-Methyl-3-o-tolyl-propan-1-ol (2j). Colorless oil. Yield: 157.5
mg, 96%. 1H NMR (400 MHz, CDCl3) δ 7.25−7.21 (m, 4H), 3.64−
3.53 (m, 2H), 2.89−2.84 (m, 2H), 2.49−2.35 (m, 4H), 2.07−1.97
(m, 1H), 1.03 (d, J = 6.7 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ
139.0, 136.3, 130.4, 13.0, 126.1, 125.8, 67.9, 37.0, 36.7, 19.6, 16.7.
2-Methyl-3-m-tolyl-propan-1-ol (2k). Colorless oil. Yield: 154.2
1
mg, 94%. H NMR (400 MHz, CDCl3) δ 7.26 (t, J = 7.5 Hz, 1H),
7.11−7.06 (m, 3H), 3.62−3.51 (m, 2H), 2.82 (dd, J = 13.4, 6.1 Hz,
2H), 2.45−2.42 (m, 4H), 2.04−1.96 (m, 1H), 1.00 (d, J = 6.7 Hz,
3H); 13C NMR (100 MHz, CDCl3) δ 140.8, 137.8, 130.1, 128.2,
126.7, 126.3, 67.6, 39.75 (s), 37.9, 21.5, 16.6.
2-Methyl-3-p-tolyl-propan-1-ol (2l). Colorless oil. Yield: 152.6
mg, 93%. 1H NMR (400 MHz, CDCl3) δ 7.20−7.15 (m, 4H), 3.61−
3.50 (m, 2H), 2.92 (s, 1H), 2.85−2.80 (m, 1H), 2.47−2.42 (m, 4H),
2.02−1.96 (m, 1H), 1.00 (br, 3H); 13C NMR (101 MHz, CDCl3) δ
137.7, 135.3, 129.2, 129.0, 67.6, 39.3, 37.9, 21.1, 16.6.
3-(2-Methoxy-phenyl)-2-methyl-propan-1-ol (2m). Colorless oil.
Yield: 174.7 mg, 97%. 1H NMR (400 MHz, CDCl3) δ 7.16−7.11 (m,
1H), 7.08 (d, J = 7.3 Hz, 1H), 6.85 (t, J = 7.4 Hz, 1H), 6.79 (d, J = 8.2
Hz, 1H), 3.72 (s, 3H), 3.42−3.34 (m, 2H), 3.27 (s, 1H), 2.71 (dd, J =
13.3, 6.7 Hz, 1H), 2.45 (dd, J = 13.3, 7.3 Hz, 1H), 1.96−1.91 (m,
1H), 0.90 (d, J = 6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 157.6,
131.2, 129.0, 127.3, 120.6, 110.4, 67.1, 55.3, 36.6, 33.5, 16.9.
3-(3-Methoxy-phenyl)-2-methyl-propan-1-ol (2n). Colorless oil.
Yield: 171.1 mg, 95%. 1H NMR (400 MHz, CDCl3) δ 7.24−7.20 (m,
1H), 6.80−6.76 (m, 3H), 3.81 (s, 3H), 3.58−3.46 (m, 2H), 2.77 (dd,
J = 13.4, 6.2 Hz, 1H), 2.40 (dd, J = 13.4, 8.3 Hz, 1H), 2.18 (s, 1H),
2.00−1.94 (m, 1H), 0.93 (d, J = 6.7 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 159.5, 142.3, 129.2, 121.6, 114.9, 111.1, 67.7, 55.2, 39.8,
37.7, 16.5.
3-Phenyl-propan-1-ol (2a). Colorless oil. Yield: 126.5 mg, 93%.
1H NMR (400 MHz, CDCl3) δ 7.35−7.32 (m, 2H), 7.26−7.22 (m,
3H), 3.70 (t, J = 6.5 Hz, 2H), 2.74 (t, J = 8.0 Hz, 2H), 2.24 (s, 1H),
1.97−1.89 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 141.9, 128.5,
128.4, 125.9, 62.2, 34.2, 32.1.
3-p-Tolyl-propan-1-ol (2b). Colorless oil. Yield: 141.1 mg, 94%.
1H NMR (400 MHz, CDCl3) δ 7.15−7.13 (m, 4H), 3.70 (t, J = 6.5
Hz, 2H), 2.71 (t, J = 8.0 Hz, 2H), 2.38 (s, 3H), 2.10 (s, 1H), 1.95−
1.88 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 138.8, 135.3, 129.1,
128.4, 62.2, 34.4, 31.7, 21.1.
3-(4-Methoxy-phenyl)-2-methyl-propan-1-ol (2o). Colorless oil.
Yield: 169.3 mg, 94%. 1H NMR (400 MHz, CDCl3) δ 7.12 (d, J = 8.5
Hz, 2H), 6.86 (d, J = 8.6 Hz, 2H), 3.80 (s, 3H), 3.55−3.44 (m, 2H),
3.07 (s, 1H), 2.75 (dd, J = 13.5, 6.0 Hz, 1H), 2.37 (dd, J = 13.5, 8.2
Hz, 1H), 1.92 (dq, J = 13.0, 6.4 Hz, 1H), 0.93 (d, J = 6.8 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ 157.8, 132.8, 130.1, 113.7, 67.4, 55.2,
38.8, 37.9, 16.4.
3-(4-Dimethylamino-phenyl)-propan-1-ol (2c). Colorless oil.
1
Yield: 171.8 mg, 96%. H NMR (400 MHz, CDCl3) δ 7.14−7.44
(m, 2H), 6.78−6.74 (m, 2H), 3.69 (t, J = 6.5 Hz, 2H), 2.95 (s, 6H),
2.65 (t, J = 8.0 Hz, 2H), 2.00 (s, 1H), 1.92−1.85 (m, 2H); 13C NMR
(100 MHz, CDCl3) δ 149.1, 130.2, 129.1, 113.3, 62.4, 41.1, 34.5, 31.1.
3-(4-Fluoro-phenyl)-propan-1-ol (2d). Colorless oil. Yield: 151.0
mg, 98%. 1H NMR (400 MHz, CDCl3) δ 7.17−7.13 (m, 2H), 7.00−
6.95 (m, 2H), 3.65 (t, J = 6.5 Hz, 2H), 2.83 (s, 1H), 2.68 (t, J = 8.0
Hz, 2H), 1.90−1.83 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 162.5,
160.1, 137.5, 137.5, 129.8, 129.7, 115.2, 115.0, 61.8, 34.3, 31.2.
3-(2-Chloro-phenyl)-propan-1-ol (2e). Colorless oil. Yield: 161.5
mg, 95%. 1H NMR (400 MHz, CDCl3) δ 7.39−7.26 (m, 5H), 4.28−
4.22 (m, 1H), 3.86−3.81 (m, 1H), 3.75−3.69 (m, 1H), 3.20−3.15
(m, 1H), 3.11−3.05 (m, 1H), 2.39 (s, 1H); 13C NMR (100 MHz,
CDCl3) δ 137.2, 129.4, 128.6, 127.0, 65.9, 64.9, 40.79.
3-(4-Chlorophenyl)-2-methylpropan-1-ol (2p). Colorless oil.
1
Yield: 176.7 mg, 96%. H NMR (400 MHz, CDCl3) δ 7.25 (d, J =
8.4 Hz, 2H), 7.10 (d, J = 8.4 Hz, 2H), 3.75 (s, 1H), 3.51−3.43 (m,
2H), 2.76 (dd, J = 13.5, 5.9 Hz, 1H), 2.35 (dd, J = 13.5, 8.4 Hz, 1H),
1.93−1.84 (m, 2H), 0.90 (d, J = 6.8 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 139.2, 131.5, 130.6, 128.3, 67.1, 38.9, 37.7, 16.3.
1
2-Benzyl-butan-1-ol (2q). Colorless oil. Yield: 149.3 mg, 91%. H
NMR (400 MHz, CDCl3) δ 7.35−7.31 (m, 2H), 7.25−7.22 (m, 3H),
3.57 (d, J = 5.4 Hz, 2H), 2.69−2.66 (m, 2H), 1.85 (s, 1H), 1.80−1.74
(m, 1H), 1.48−1.38 (m, 2H), 0.98 (t, J = 7.5 Hz, 3H); 13C NMR
(102 MHz, CDCl3) δ 140.9, 129.2, 128.3, 125.9, 64.4, 44.1, 37.3, 23.3,
11.4.
2-Benzyl-heptan-1-ol (2r). Colorless oil. Yield: 189.7 mg, 92%. 1H
NMR (400 MHz, CDCl3) δ 7.46−6.99 (m, 7.3H), 6.51 (s, 0.4H),
4.20 (s, 0.8H), 3.50 (d, J = 5.3 Hz, 2H), 2.62 (dd, J = 7.1, 3.1 Hz,
2H), 2.29−2.25 (m, 0.9H), 1.82−1.74 (m, 1H), 1.53−1.44 (m, 9H),
1.40−1.18 (m, 10.4H), 0.87 (br, 4.3H); 13C NMR (101 MHz,
CDCl3) δ 142.5, 140.9, 137.7, 129.2, 128.7, 128.3, 128.2, 126.4, 125.9,
125.2, 66.9, 64.8, 42.6, 37.7, 32.2, 32.1, 30.8, 28.8, 28.1, 26.7, 22.7,
22.5, 14.1, 14.0.
3-(3-Chloro-phenyl)-ropan-1-ol (2f). Colorless oil. Yield: 159.8
mg, 94%. 1H NMR (400 MHz, CDCl3) δ 7.23−7.20 (m, 3H), 7.11−
7.08 (m, 1H), 3.68 (t, J = 6.4 Hz, 2H), 2.72−2.69 (m, 2H), 1.91−
1.85 (m, 3H); 13C NMR (100 MHz, CDCl3) δ 143.9, 134.1, 129.7,
128.6, 126.7, 126.1, 61.9, 33.9, 31.7.
3-(4-Chloro-phenyl)-propan-1-ol (2g). Colorless oil. Yield: 163.2
1
mg, 96%. H NMR (400 MHz, CDCl3) δ 7.25 (d, J = 8.4 Hz, 2H),
1
7.12 (d, J = 8.3 Hz, 2H), 3.63 (t, J = 6.5 Hz, 2H), 3.27 (s, 1H), 2.66
(d, J = 8.0 Hz, 2H), 1.88−1.81 (m, 2H); 13C NMR (100 MHz,
CDCl3) δ 140.4, 131.5, 129.8, 128.5, 61.7, 34.0, 31.4.
2-Benzyl-octan-1-ol (2s). Colorless oil. Yield: 200.4 mg, 91%. H
NMR (400 MHz, CDCl3) δ 7.37−7.21 (m, 7.7H), 6.56 (s, 0.5H),
4.25 (d, J = 1.3 Hz, 1H), 3.55 (d, J = 5.3 Hz, 2H), 2.67 (dd, J = 7.1,
2.2 Hz, 2H), 2.32 (br, 1H), 1.84−1.79 (m, 1.6H), 1.55−1.49 (m,
1H), 1.38−1.30 (m, 14H), 0.94−0.89 (m, 3.0 Hz, 4.8H); 13C NMR
(101 MHz, CDCl3) δ 142.5, 140.9, 137.6, 129.2, 128.7, 128.3, 128.2,
126.5, 125.9, 125.2, 67.0, 64.8, 42.6, 37.7, 31.9, 31.6, 30.8, 29.6, 29.6,
28.8, 28.4, 27.0, 22.7, 22.7, 14.2, 14.1.
3-Furan-2-yl-propan-1-ol (2h). Light yellow oil. Yield: 113.4 mg,
1
90%. H NMR (400 MHz, CDCl3) δ 7.29 (br, 1H), 6.28−6.27 (m,
1H), 6.00 (d, J = 2.9 Hz, 1H), 3.66 (t, J = 6.4 Hz, 2H), 2.72 (t, J = 7.5
Hz, 2H), 1.93−1.86 (m, 3H); 13C NMR (100 MHz, CDCl3) δ 155.6,
140.9, 110.1, 105.0, 61.9, 30.9, 24.3.
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Organometallics XXXX, XXX, XXX−XXX