10.1002/chem.202002792
Chemistry - A European Journal
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6H), 6.89-6.87 (m, 2H), 6.01-5.97 (d, J = 16.0 Hz, 1H), 4.25-4.20 (q, J =
6.7 Hz, 2H), 1.33-1.29 (t, J = 8.0 Hz, 3H) ppm.
Keywords: catalytic arsa-Wittig reaction • iron-free • silane
agent • E/Z selectivity • density functional theory
(E)-Ethyl-3-(naphthalene-2-yl)prop-2-enoate (18).[27h] Product: 198 mg,
0.874 mmol, 87%. 2-Naphthaldehyde (157 mg, 1.00 mmol), ethyl
bromoacetate (200 mg, 1.20 mmol), Ph3SiH (312 mg, 1.20 mmol),
diisopropylethylamine (155 mg, 1.20 mmol) and 1-phenylarsolane (5, 21
mg, 0.10 mmol) were used. 1H-NMR (CDCl3, 400 MHz): δ 8.55-8.51 (d, J
= 16.0 Hz, 1H), 8.21-8.19 (d, J = 12.0 Hz, 1H), 7.90-7.86 (t, J = 8.0 Hz,
2H), 7.76-7.74 (d, J = 8.0 Hz, 1H), 7.59-7.46 (m, 3H), 6.55-6.51 (d, J =
16.0 Hz, 1H), 4.33-4.29 (q, J = 5.3 Hz, 2H), 1.39-1.36 (t, J = 6.0 Hz, 3H)
ppm.
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(E)-3-(9H-Fluoren-2-yl)-2-propenoic acid ethyl ester (19). Product: 214 mg,
0.808 mmol, 81%. 2-Fluorenecarboxaldehyde (194 mg, 1.00 mmol), ethyl
bromoacetate (201 mg, 1.20 mmol), Ph3SiH (313 mg, 1.20 mmol),
diisopropylethylamine (155 mg, 1.20 mmol) and 1-phenylarsolane (5, 20
mg, 0.099 mmol) were used. 1H-NMR (CDCl3, 400 MHz): δ 7.79-7.72 (m,
4H), 7.57-7.55 (m, 2H), 7.41-7.32 (m, 2H), 6.50-6.46 (d, J = 16.0 Hz, 1H),
4.31-4.26 (q, J = 6.7 Hz, 2H), 3.93 (s, 2H), 1.37-1.34 (t, J = 6.0 Hz, 3H)
ppm. 13C{1H}-NMR (CDCl3, 100 MHz): δ 167.21, 144.97, 144.00, 143.85,
143.79, 140.92, 133.04, 127.47, 127.43, 126.99, 125.16, 124.48, 120.35,
120.18, 117.34, 60.44, 36.81, 14.37 ppm.
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(E)-Ethyl-3-(2-thiophene)acrylate (21).[27g] Product: 152 mg, 0.834 mmol,
83%. 2-Thiophenecarboxyaldehyde (112 mg, 1.00 mmol), ethyl
bromoacetate (201 mg, 1.20 mmol), Ph3SiH (313 mg, 1.20 mmol),
diisopropylethylamine (155 mg, 1.20 mmol) and 1-phenylarsolane (5, 21
mg, 0.10 mmol) were used. 1H-NMR (CDCl3, 400 MHz): δ 7.80-7.76 (d, J
= 16.0 Hz, 1H),7.37-7.36 (d, J = 4.0 Hz, 1H),7.25-7.24 (d, J = 4.0 Hz, 1H),
7.06-7.04 (m, 1H), 6.26-6.22 (d, J = 16.0 Hz, 1H), 4.27-4.22 (q, J = 6.7 Hz,
2H), 1.34-1.31 (t, J = 6.0 Hz, 3H) ppm.
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(E)-Methylcinnamate (22).[27a] A Schlenk tube with a stirring bar was
charged with benzaldehyde (107 mg, 1.0 mmol), methyl bromoacetate
(184 mg, 1.2 mmol), Ph3SiH (313 mg, 1.2 mmol), diisopropylethylamine
(155 mg, 1.2 mmol) and 1-phenylarsolane (5, 21 mg, 0.10 mmol, 10 mol%).
The tube was then purged with N2 and they were dissolved in toluene (1.0
mL). The mixture was heated at 100 °C for 24 h. After cooling to room
temperature, the solvent was removed in vacuo. The residue was dried
under vacuum, and then subjected to silica column chromatography
(eluent: hexane/EtOAc = 15:1). The solvent was removed in vacuo to
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1
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afford 22 (122 mg, 0.75 mmol, 75%) as a colorless oil. H-NMR (CDCl3,
400 MHz): δ 7.72-7.68 (d, J = 16.0 Hz, 1H), 7.53-7.50 (m, 2H), 7.39-7.36
(t, J = 6.0 Hz, 3H), 6.47-6.43 (d, J = 16.0 Hz, 1H), 3.81 (s, 3H) ppm.
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The experimental procedure and evaluation method for the reaction rate
of the reduction of 3-oxide and 5-oxide. Arsine oxide (0.10 mmol) was
charged with 30 mL two-necked round bottom flask, and then purged with
N2. Arsine oxide was dissolved with toluene (1.0 mL), and heated at 100 °C.
Next, Ph3SiH (1.2 mmol, 0.313 g) was dissolved with toluene (1.0 mL) at
100 °C, and the resultant solution was added to arsine oxide solution at
one portion. The collecting reaction mixture for 3, 9 and 15 min later was
quenched with ice bath, and instantly removed the solvent in vacuo. The
residue was dried under vacuum. The products were dissolved with CDCl3,
and used for 1H-NMR analysis.
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Acknowledgements
H.I. acknowledged
a
JSPS KAKENHI Grant Number
JP19H04577 (Coordination Asymmetry).
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