Page 21 of 31
The Journal of Organic Chemistry
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CH2), 1.94–1.88 (m, 1 H, CH2), 1.73 (s, 3 H, CH3), 1.59–1.50 (m, 2 H, CH2), 1.40 (sext, 2 H,
3JH,H = 7.4 Hz, CH2), 0.97 ppm (t, 3 H, 3JH,H = 7.3 Hz, CH3). 13C{1H} NMR (151 MHz, CDCl3):
ꢀ = 133.1 (q, Car), 132.8 (q, Car), 131.4 (t, CarH), 128.7 (t, CarH), 128.0 (t, CarH), 127.9 (t,
CarH), 127.8 (t, CarH), 126.6 (t, CarH), 120.8 (q, Car), 86.2 (q, C≡C), 83.6 (q, C≡C), 71.8 (q, C-
Cl), 43.0 (s, CH2), 35.8 (s, CH2), 30.0 (p, CH3), 27.0 (s, CH2), 22.9 (s, CH2), 14.2 ppm (p,
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ꢁ
CH3). IR (ATR): v = 3057, 2955, 2930, 1628, 1597, 1501, 1456, 1429, 1379, 1343, 1261,
1221, 1126, 1044, 891, 856, 816, 745, 635 cm−1. UV/Vis (CH3CN): ꢂmax (log ꢃ) = 245 (4.78),
276 (4.03), 286 (4.08), 297 (3.94), 316 nm (3.07). HRMS (ESI) m/z: [M + H]+ Calcd for
C19H2235Cl 285.1405; Found 285.1399, [M – Cl]+ Calcd for C19H21 249.1638; Found 249.1630.
Synthesis of 1-(3-(1-chlorocyclohexyl)prop-1-yn-1-yl)-4-fluorobenzene (14e). According
to the general procedure, chloroarylacetylene 3e (61.8 mg, 400 µmol, 1.0 eq) and
methylencyclohexane (384.7 mg, 4 mmol, 481 µL, 10.0 eq) were dissolved in dry DCM (4
mL). Then [JohnPhosAu(NCMe)]SbF6 (5 mol%, 20 µmol, 15.4 mg) was added. The reaction
mixture was stirred at room temperature for three days. After removing the solvent and
excess alkene in vacuo, the residue was purified by flash chromatography (SiO2, n-hexane)
to yield 14e (63.6 mg, 254 µmol, 64%) as a colorless oil. Rf (n-hexane) = 0.23. 1H NMR (600
MHz, CDCl3): ꢀ = 7.43–7.38 (m, 2 H, CHar), 7.02–6.96 (m, 2 H, CHar), 2.91 (s, 2 H, CH2),
2.07–1.99 (m, 2 H, CH2), 1.82–1.74 (m, 4 H, CH2), 1.73–1.67 (m, 1 H, CH2), 1.66–1.60 (m, 2
H, CH2), 1.26–1.18 ppm (m, 1 H, CH2). 19F NMR (565 Hz, CDCl3): ꢀ = −111.6 ppm (m, 1 F,
CFar). 13C{1H} NMR (151 MHz, CDCl3): ꢀ = 162.4 (q, JC,F = 248.8 Hz, CarF), 133.6 (t, 3JC,F
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=
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8.2 Hz, CarH), 119.7 (q, JC,F = 3.3 Hz, CarF), 115.6 (t, JC,F = 22.0 Hz, CarH), 85.3 (q, C≡C),
82.5 (q, C≡C), 73.1 (q, C-Cl), 39.0 (s, CH2), 37.0 (s, CH2), 25.3 (s, CH2), 22.4 ppm (s, CH2).
ꢁ
IR (ATR): v = 2934, 2862, 1601, 1506, 1447, 1427, 1229, 1155, 1126, 1092, 1015, 932, 876,
833, 814, 783, 669 cm−1. UV/Vis (CH3CN): ꢂmax (log ꢃ) = 200 (4.37), 238 nm (4.14). HRMS
(APCI) m/z: [M + H]+ Calcd for C15H1735ClF 251.0997; Found 251.1011.
Synthesis of 1-(4-chloro-4-methyloct-1-yn-1-yl)-2-methylbenzene (14f). According to the
general procedure, chloroarylacetylene 3f (54.0 mg, 359 µmol, 1.0 eq) and 2-methyl-1-
hexene (13b) (352.5 mg, 3.6 mmol, 503 µL, 10.0 eq) were dissolved in dry DCM (3.6 mL).
Then [JohnPhosAu(NCMe)]SbF6 (5 mol%, 18 µmol, 13.9 mg) was added. The reaction
mixture was stirred at room temperature for four days. After removing the solvent and excess
alkene in vacuo, the residue was purified by flash chromatography (SiO2, n-hexane) to yield
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14f (49.9 mg, 201 µmol, 56%) as a colorless oil. Rf (n-hexane) = 0.26. H NMR (600 MHz,
CDCl3): ꢀ = 7.40–7.36 (m, 1 H, CHar), 7.22–7.17 (m, 2 H, CHar), 7.14–7.10 (m, 1 H, CHar),
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2.97 (d, 1 H, JH,H = 16.9 Hz, CH2), 2.94 (d, 1 H, JH,H = 16.9Hz, CH2), 2.43 (s, 3 H, CH3),
2.00–1.93 (m, 1 H, CH2), 1.92–1.86 (m, 1 H, CH2), 1.70 (s, 3 H, CH3), 1.54–1.48 (m, 2 H,
CH2), 1.37 (sext, 2 H, JH,H = 7.4 Hz, CH2), 0.95 ppm (t, 3 H, JH,H = 7.3 Hz, CH3). 13C{1H}
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NMR (151 MHz, CDCl3): ꢀ = 140.3 (q, CarCH3), 132.1 (t, CarH), 129.5 (t, CarH), 128.1 (t,
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