K. Junge, B. Wendt, S. Zhou, M. Beller
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the reaction was initiated by the addition of PMHS (180 μL,
3 equiv.). The reaction mixture was placed in a preheated oil bath
(100 °C) for 20 h. Then, hexadecane (GC internal standard, 100 μL
per 1 mmol ester) was added at room temperature. The reaction
mixture was diluted with THF (4 mL) and carefully quenched with
NaOH (25% in MeOH, 300 μL). Caution: The reaction mixture
bubbles vigorously! Conversion and yield were determined by GC
analysis without further manipulations and compared with authen-
tic samples. The yield was determined by GC (30 m HP 5 Agilent
Technologies 50–300 °C) on the basis of an internal standard (cali-
bration curve). For isolated yields, the catalytic reaction was re-
peated on a 4–5 mmol substrate scale. After basic quenching of the
reaction mixture, the solvents were evaporated. The crude product
was purified by column chromatography (pentane/diethyl ether,
4:1Ǟ2:1Ǟ1:1).
2-Phenylethanol (3b): Yield: 318 mg (4 mmol scale), 65% (isolated).
1H NMR (300 MHz, CDCl3): δ = 7.28–7.20 (m, 2 H, C6H5), 7.19–
7.11 (m, 3 H, C6H5), 3.76 (t, J = 6.6 Hz, 2 H, CH2), 2.78 (t, J =
6.5 Hz, 2 H, CH2) 1.57 (s, 1 H, OH) ppm. 13C NMR (75 MHz,
CDCl3): δ = 138.5 (i-C6H5), 129.1 (m-C6H5), 128.6 (o-C6H5), 126.5
(p-C6H5), 61 (CH2), 38 (CH2) ppm. MS (EI): m/z (%) = 122 (22)
[M]+, 103 (3), 91 (100), 77 (6), 65 (23), 63 (9), 51 (10), 39 (12), 31
(7).
2-(4-tert-Butylphenyl)ethanol (3h): Yield: 721 mg (5 mmol scale),
81% (isolated). 1H NMR (300 MHz, CDCl3): δ = 7.36 (d, J =
8.4 Hz, 2 H, C6H4), 7.18 (d, J = 8.4 Hz, 2 H, C6H4), 3.86 (t, J =
6.7 Hz, 2 H, CH2), 2.86 (t, J = 6.6 Hz, 2 H, CH2), 1.65 (s, 1 H,
OH), 1.34 (s, 9 H, t-C4H9) ppm. 13C NMR (75 MHz, CDCl3): δ =
149.4 (p-C6H4), 135.4 (i-C6H4), 128.8 (o-C6H4), 125.6 (m-C6H4),
63.7 (CH2), 38.7 (CH2), 34.5 (C-CH3), 31.4 (C-CH3) ppm. MS (EI):
m/z (%) = 178 (18) [M]+, 163 (100), 147 (14), 132 (11), 117 (30),
143 (8), 105 (15), 91 (19),77 (6), 65 (5), 57 (3), 51 (3), 41 (7), 31 (8).
[7]
2-(4-Fluorophenyl)ethanol (3i): Yield: 507 mg (5 mmol scale), 72%
(isolated). 1H NMR (300 MHz, CDCl3): δ = 7.22–7.15 (m, 2 H,
C6H4), 7.04–6.96 (m, 2 H, C6H4), 3.82 (t, J = 6.6 Hz, 2 H, CH2),
2.83 (t, J = 6.5 Hz, 2 H, CH2), 1.8 (s, 1 H, OH) ppm. 13C NMR
(75 MHz, CDCl3): δ = 161.5 (d, J = 243.8 Hz, p-C6H4), 134.2 (d,
J = 3.2 Hz, i-C6H4), 130.4 (d, J = 8.0 Hz, o-C6H4), 115.3 (d, J =
21.7 Hz, m-C6H4), 63.6 (CH2), 38.4 (CH2) ppm. MS (EI): m/z (%)
= 140 (16) [M]+, 122, (2), 109 (100), 101 (1), 96 (3), 89 (3), 83 (19),
75 (3), 63 (6), 57 (7), 51 (4), 39 (4), 31 (7), 29 (3).
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Acknowledgments
The authors thank Dr. C. Fischer, S. Buchholz, S. Schareina, K.
Fiedler, and S. Rossmeisl (all at the Leibniz-Institut für Katalyse
e.V.) for excellent analytical and technical support.
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