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Z. Li et al.
Paper
Synthesis
1H NMR (501 MHz, CDCl3): = 8.15 (d, J = 7.7 Hz, 2 H), 7.67–7.60 (m, 1
H), 7.50 (t, J = 7.7 Hz, 2 H), 7.28 (d, J = 8.6 Hz, 1 H), 6.97 (dt, J = 8.7, 2.8
Hz, 1 H), 6.92 (s, 1 H), 6.34 (d, J = 60.8 Hz, 1 H), 2.92 (dd, J = 9.8, 4.5 Hz,
2 H), 2.50 (dd, J = 19.0, 8.7 Hz, 1 H), 2.44–2.37 (m, 1 H), 2.27 (td, J =
10.8, 4.3 Hz, 1 H), 2.14 (dt, J = 18.5, 8.9 Hz, 1 H), 2.10–1.98 (m, 2 H),
2.00–1.93 (m, 1 H), 1.67–1.55 (m, 2 H), 1.57–1.39 (m, 4 H), 0.91 (s, 3
H).
13C NMR (126 MHz, CDCl3): = 187.52 (d, J = 28.5 Hz), 164.49, 156.45,
150.08 (d, J = 2.7 Hz), 132.45 (d, J = 1.8 Hz), 125.34, 118.88, 114.84,
114.04, 108.55 (d, J = 234.1 Hz), 55.66, 55.58.
19F NMR (376 MHz, CDCl3): = –124.77 (d, J = 62.2 Hz).
HRMS (ESI-TOF): m/z [M + Na]+ calcd for C16H15FO4Na: 313.0846;
found: 313.0844.
13C NMR (126 MHz, CDCl3): = 220.68, 188.82 (d, J = 28.3 Hz), 154.04
(d, J = 2.9 Hz), 138.58, 136.06, 134.35, 132.42, 129.95 (d, J = 1.6 Hz),
128.74, 126.87, 117.42 (d, J = 8.0 Hz), 114.67, 107.33 (d, J = 232.9 Hz),
50.42, 47.96, 44.06, 38.15, 35.86, 31.58, 29.57, 26.38, 25.87, 21.60,
13.86.
2-Fluoro-1-(2-fluorophenyl)-2-(4-methoxyphenoxy)ethan-1-one
(5v)
Purified by flash column chromatography on silica gel (PE/EtOAc =
20:1).
Yield: 49.5 mg (89%); light yellow oil.
19F NMR (376 MHz, CDCl3): = –126.02 (d, J = 59.8 Hz).
1H NMR (501 MHz, CDCl3): = 7.99 (t, J = 7.5 Hz, 1 H), 7.60 (q, J = 7.3
Hz, 1 H), 7.29 (t, J = 7.6 Hz, 1 H), 7.21–7.13 (m, 1 H), 7.10 (d, J = 9.3 Hz,
2 H), 6.86 (dd, J = 8.9, 1.7 Hz, 2 H), 6.39 (dd, J = 61.5, 2.7 Hz, 1 H), 3.78
(s, 3 H).
13C NMR (126 MHz, CDCl3): = 187.56 (dd, J = 26.8, 3.7 Hz), 161.94 (d,
J = 256.0 Hz), 156.51, 150.25 (d, J = 2.9 Hz), 136.04 (d, J = 9.4 Hz),
131.56, 124.91 (d, J = 3.4 Hz), 122.24 (d, J = 13.3 Hz), 118.97, 116.67
(d, J = 23.1 Hz), 114.80, 106.57 (dd, J = 231.3, 7.2 Hz), 55.65.
HRMS (ESI-TOF): m/z [M + NH4]+ calcd for C26H31FO3N: 424.2282;
found: 424.2283.
2-Fluoro-1-(furan-2-yl)-2-(4-methoxyphenoxy)ethan-1-one (5s)
Purified by flash column chromatography on silica gel (PE/EtOAc =
100:1).
Yield: 45.0 mg (90%); yellow oil.
1H NMR (501 MHz, CDCl3): = 7.64 (s, 1 H), 7.41 (d, J = 8.7 Hz, 2 H),
7.31 (d, J = 3.6 Hz, 1 H), 6.84 (d, J = 8.8 Hz, 2 H), 6.56 (dd, J = 3.7, 1.7 Hz,
1 H), 6.49 (d, J = 52.2 Hz, 1 H), 3.79 (s, 3 H).
13C NMR (126 MHz, CDCl3): = 178.44 (d, J = 25.9 Hz), 160.99, 149.45,
147.53, 136.59 (d, J =1.3 Hz), 120.55 (d, J = 4.6 Hz), 119.72, 114.84,
112.68, 98.20 (d, J = 233.8 Hz), 55.36.
19F NMR (376 MHz, CDCl3): = –108.80, –131.85 (dd, J = 61.6, 8.7 Hz).
HRMS (ESI-TOF): m/z [M + Na]+ calcd for C15H12F2O3Na: 301.0647;
found: 301.0649.
2-Fluoro-2-(4-methoxyphenoxy)-1-(3-methoxyphenyl)ethan-1-
one (5w)
19F NMR (376 MHz, CDCl3): = –127.26 (d, J = 61.1 Hz).
HRMS (ESI-TOF): m/z [M + Na]+ calcd for C13H11FO4Na: 273.0534;
Purified by flash column chromatography on silica gel (PE/EtOAc =
20:1).
found: 273.0537.
Yield: 52.8 mg (91%); colorless oil.
1H NMR (501 MHz, CDCl3): = 7.76 (d, J = 7.6 Hz, 1 H), 7.66 (s, 1 H),
7.41 (t, J = 8.0 Hz, 1 H), 7.19 (dd, J = 8.0, 2.4 Hz, 1 H), 7.12 (d, J = 8.9 Hz,
2 H), 6.88 (d, J = 9.0 Hz, 2 H), 6.25 (d, J = 60.9 Hz, 1 H), 3.86 (s, 3 H),
3.80 (s, 3 H).
13C NMR (126 MHz, CDCl3): = 188.75 (d, J = 28.4 Hz), 159.87, 156.59,
150.05 (d, J = 2.8 Hz), 133.72, 129.77, 122.67 (d, J = 2.5 Hz), 121.09,
118.98, 114.92, 113.89, 108.16 (d, J = 234.0 Hz), 55.70, 55.53.
2-Fluoro-2-(4-methoxyphenoxy)-1-(naphthalen-1-yl)ethan-1-one
(5t)
Purified by flash column chromatography on silica gel (PE/EtOAc =
100:1).
Yield: 54.6 mg (88%); yellow oil.
1H NMR (501 MHz, CDCl3): = 8.30–8.24 (m, 1 H), 8.04 (d, J = 8.2 Hz, 1
H), 7.94 (d, J = 7.2 Hz, 1 H), 7.93–7.84 (m, 1 H), 7.57–7.51 (m, 2 H),
7.50 (dd, J = 8.2, 7.3 Hz, 1 H), 7.38–7.30 (m, 2 H), 6.82 (d, J = 52.2 Hz, 1
H), 6.84–6.77 (m, 2 H), 3.79 (s, 3 H).
13C NMR (126 MHz, CDCl3): = 192.16 (d, J = 23.3 Hz), 160.93, 136.44,
134.03, 133.98, 131.52, 130.70, 128.57, 128.35 (d, J = 1.6 Hz), 128.21,
126.78, 125.67, 124.15, 119.91, 114.82, 98.60 (d, J = 234.5 Hz), 55.40.
19F NMR (376 MHz, CDCl3): = –125.42 (d, J = 60.5 Hz).
HRMS (ESI-TOF): m/z [M + Na]+ calcd for C16H15FO4Na: 313.0846;
found: 313.0849.
2-Fluoro-2-(4-methoxyphenoxy)-1-[4-(trifluoromethyl)-
phenyl]ethan-1-one (5x)
19F NMR (376 MHz, CDCl3): = –123.82 (d, J = 61.2 Hz).
HRMS (ESI-TOF): m/z [M + Na]+ calcd for C19H15FO3Na: 333.0897;
Purified by flash column chromatography on silica gel (PE/EtOAc =
20:1).
found: 333.0893.
Yield: 114.2 mg (87%); light yellow solid; mp 74.2–74.5 °C.
1H NMR (501 MHz, CDCl3): = 8.30 (d, J = 8.1 Hz, 2 H), 7.78 (d, J = 8.2
Hz, 2 H), 7.12 (d, J = 8.9 Hz, 2 H), 6.89 (d, J = 9.2 Hz, 2 H), 6.22 (d, J =
60.8 Hz, 1 H), 3.80 (s, 3 H).
13C NMR (126 MHz, CDCl3): = 188.22 (d, J = 30.0 Hz), 156.77, 149.86
(d, J = 2.8 Hz), 135.38 (q, J = 32.9 Hz), 130.45 (d, J = 2.4 Hz), 125.73 (q,
J = 3.6 Hz), 123.52 (q, J = 273.0 Hz), 118.91, 114.98, 108.66 (d, J = 234.1
Hz), 55.66.
2-Fluoro-2-(4-methoxyphenoxy)-1-(4-methoxyphenyl)ethan-1-
one (5u)
Purified by flash column chromatography on silica gel (PE/EtOAc =
20:1).
Yield: 42.8 mg (91%); light yellow solid; mp 77.6–77.8 °C.
1H NMR (501 MHz, CDCl3): = 8.15 (d, J = 8.7 Hz, 2 H), 7.12 (d, J = 9.0
Hz, 2 H), 6.98 (d, J = 9.0 Hz, 2 H), 6.88 (d, J = 9.0 Hz, 2 H), 6.22 (d, J =
61.1 Hz, 1 H), 3.88 (s, 3 H), 3.79 (s, 3 H).
19F NMR (376 MHz, CDCl3): = –63.36, –124.22 (d, J = 60.8 Hz).
HRMS (ESI-TOF): m/z [M + Na]+ calcd for C16H12F4O3Na: 351.0615;
found: 351.0613.
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