FULL PAPER
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acetate/petroleum ether (1:20,
R
f
=0.30).
H
NMR
S-(fluoromethyl) dodecanethioate (3x). Colourless oil
1
(
400 MHz, CDCl ) d 8.38 (s, 1H), 8.21–8.16 (m, 1H), 7.97–
.93 (m, 1H), 7.86–7.83 (m, 2H), 7.43–7.33 (m, 2H), 7.29 (d,
J=8.3 Hz, 2H), 6.02 (d, J=50.4 Hz, 2H), 2.36 (s, 3H) ppm;
(38.8 mg, 78%). Eluant: petroleum ether (R =0.50). H
f
3
7
NMR (400 MHz, CDCl ) d 5.80 (d, J=50.3 Hz, 2H), 2.86–
3
2.50 (m, 2H), 1.81–1.64 (m, 2H), 1.45–1.19 (m, 16H), 0.88 (t,
19
19
F NMR (375 MHz, CDCl ) d À190.72 (t, J=50.4 Hz, 1F)
J=6.8 Hz, 3H) ppm; F NMR (375 MHz, CDCl ) d À192.16
3
3
1
3
13
ppm; C NMR (100 MHz, CDCl ) d 181.0 (d, J=1.7 Hz),
(t, J=50.3 Hz, 1F) ppm; C NMR (100 MHz, CDCl ) d 195.8
3
3
1
1
(
46.3, 134.7, 134.2, 131.9, 130.4, 127.3, 126.7, 126.2, 125.1,
22.4, 120.1, 113.3, 80.5 (d, J=216.1 Hz), 21.7 ppm. IR
KBr): n=3110, 3053, 2921, 2854, 1686, 1659, 1593, 1527,
444, 1383, 1290, 1173, 968, 833, 721, 658 cm . HRMS (ESI)
(d, J=1.6 Hz), 80.9 (d, J=213.9 Hz). 44.5, 32.0, 29.7, 29.6,
29.5, 29.4, 29.3, 28.9, 25.2, 22.8, 14.3 ppm. IR (KBr): n=3411,
À1
2926, 2854, 1718, 1461, 1321, 1128, 993, 910, 737 cm . HRMS
À1
+
1
(ESI) for C H FOSNa (M+Na ): Calcd: 271.1502; Found:
1
3
25
1
1
1
1
1
1
1
1
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1
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5
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5
5
5
5
5
+
for C H FNO S (M+H ): Calcd: 364.0472; Found:
271.1511.
1
7
15
3 2
364.0480.
S-(fluoromethyl) cyclohexanecarbothioate (3y). Colourless
1
S-(fluoromethyl)
1-(phenylsulfonyl)-1H-pyrrole-2-carbo-
thioate (3t). White solid (38.8 mg, 65%). Mp: 97–988C.
Eluant: ethyl acetate/petroleum ether (1:15, R =0.30). H
NMR (400 MHz, CDCl ) d 8.06–8.01 (dd, J=5.3, 3.4 Hz,
H), 7.83 (dd, J=3.2, 1.8 Hz, 1H), 7.68–7.61 (m, 1H), 7.55 (t,
J=7.7 Hz, 2H), 7.26 (dd, J=3.6, 2.0 Hz, 1H), 6.42–6.34 (m,
1H), 5.86 (d, J=50.4 Hz, 2H) ppm; F NMR (375 MHz,
oil (18.8 mg, 53%). Eluant: petroleum ether (R =0.50). H
f
NMR (400 MHz, CDCl ) d 5.80 (d, J=50.3 Hz, 2H), 2.63–
3
1
2.51 (m, 1H), 2.02–1.92 (m, 2H), 1.86–1.75 (m, 2H), 1.73–1.63
f
19
(m, 1H), 1.55–1.43 (m, 2H), 1.36–1.20 (m, 3H) ppm;
F
3
2
NMR (375 MHz, CDCl ) d À192.32 (t, J=50.3 Hz, 1F) ppm;
3
13
C NMR (100 MHz, CDCl ) d 199.1 (d, J=1.5 Hz), 80.7 (d,
3
1
9
J=213.6 Hz), 52.9, 29.2, 25.6, 25.4 ppm. IR (KBr): n=3345,
1
3
À1
CDCl ) d À190.91 (t, J=50.4 Hz, 1F) ppm; C NMR
2932, 2856, 1716, 1450, 1294, 1212, 965, 773, 681 cm . HRMS
3
+
(100 MHz, CDCl
) d 175.5 (d, J=1.7 Hz), 138.2, 134.3, 130.9,
(ESI) for C
199.0565.
H
13FOSNa (M+Na ): Calcd: 199.0563; Found:
3
8
130.1, 129.1, 128.5, 124.9, 111.1, 80.7 (d, J=216.1 Hz) ppm.
IR (KBr): n=3396, 3161, 3118, 3010, 2921, 2850, 1696, 1662,
533, 1421, 1371, 1190, 1136, 1062, 1014, 976, 843, 727,
S-(fluoromethyl)
(3r,5r,7r)-adamantane-1-carbothioate
1
6
3
À1
+
(3z). Colourless oil (34.2 mg, 75%). Eluant: petroleum ether
81 cm . HRMS (ESI) for C H FNO S (M+H ): Calcd:
1
2
11
3
2
1
(
R =0.50). H NMR (400 MHz, CDCl ) d 5.80 (d, J=
f
3
00.0159; Found: 300.0167.
50.3 Hz, 2H), 2.08 (s, 3H), 1.93 (d, J=2.7 Hz, 6H), 1.80-1.66
1
9
S-(fluoromethyl) furan-2-carbothioate (3u). Colourless oil
(13.6 mg, 42%). Eluant: ethyl acetate/petroleum ether (1:100,
) d 7.68–7.62 (m, 1H),
.31 (dd, J=3.6, 0.6 Hz, 1H), 6.60 (dd, J=3.6, 1.7 Hz, 1H),
(m, 6H) ppm; F NMR (375 MHz, CDCl ) d À192.56 (t, J=
3
13
50.3 Hz, 1F) ppm; C NMR (100 MHz, CDCl ) d 202.3 (d,
3
1
R
=0.30). H NMR (400 MHz, CDCl
J=1.6 Hz), 80.3 (d, J=213.2 Hz), 48.9, 39.0, 36.4, 28.1 ppm.
f
3
7
5
IR (KBr): n=3379, 2910, 2852, 2671, 1699, 1452, 1319, 1141,
1
9
À1
.98 (d, J=50.2 Hz, 2H) ppm; F NMR (375 MHz, CDCl ) d
987, 794, 737, 673 cm . HRMS (ESI) for C H FOSNa (M+
3
12 17
1
3
+
À191.67 (t, J=50.2 Hz, 1F) ppm; C NMR (100 MHz,
Na ): Calcd: 251.0876; Found: 251.0879.
CDCl ) d 176.4 (d, J=1.7 Hz), 150.0, 147.3, 117.6, 112.8, 79.9
3
S-(fluoromethyl) (1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-
(
d, J=216.0 Hz) ppm. IR (KBr): n=3334, 3108, 2934, 2855,
666, 1513, 1407, 1361, 1215, 880, 807, 723, 658 cm . HRMS
ESI) for C H FO SNa (M+Na ): Calcd: 182.9886; Found:
À1
ene-2-carbothioate (3aa). Colourless oil (26.5 mg, 62%).
1
(
1
+
Eluant: petroleum ether (R
CDCl
td, J=5.7, 1.6 Hz, 1H), 2.61–2.37 (m, 3H), 2.24–2.13 (m,
1H), 1.34 (s, 3H), 1.12 (d, J=9.3 Hz, 1H), 0.79 (s, 3H) ppm;
f
=0.50). H NMR (400 MHz,
6 5 2
) d 6.97–6.91(m, 1H), 5.87 (d, J=50.5 Hz, 2H), 2.89
3
182.9886.
(
S-(fluoromethyl) thiophene-2-carbothioate (3v). Colourless
oil (22.1 mg, 63%). Eluant: ethyl acetate/petroleum ether
1:100, R =0.30). H NMR (400 MHz, CDCl ) d 7.86 (dd, J=
.9, 1.1 Hz, 1H), 7.73 (dd, J=4.9, 1.1 Hz, 1H), 7.17 (dd, J=
1
9
F NMR (375 MHz, CDCl ) d À191.16 (t, J=50.5 Hz, 1F)
3
1
13
(
ppm; C NMR (100 MHz, CDCl ) d 186.2 (d, J=1.6 Hz),
f
3
3
3
4
147.8, 138.6, 80.7 (d, J=214.0 Hz), 41.5, 40.4, 37.9, 32.6, 31.2,
25.8, 21.0 ppm. IR (KBr): n=3327, 2923, 2819, 1678, 1612,
19
.9, 3.9 Hz, 1H), 5.99 (d, J=50.3 Hz, 2H) ppm; F NMR
13
À1
(
375 MHz, CDCl ) d À190.84 (t, J=50.4, 1F) ppm; C NMR
1465, 1172, 989, 825, 735, 629 cm . HRMS (ESI) for
3
+
(
100 MHz, CDCl ) d 179.8 (d, J=1.7 Hz), 140.8, 134.5, 132.7,
C H FOSNa (M+Na ): Calcd: 237.0720; Found: 237.0726.
3
11 15
1
2
28.3, 80.8 (d, J=216.5 Hz) ppm. IR (KBr): n=3315, 3104,
953, 2854, 1957, 1664, 1512, 1412, 1352, 1211, 989, 881, 808,
729, 661 cm . HRMS (ESI) for C H FOS Na (M+Na ):
S-(fluoromethyl) (E)-oct-2-enethioate (3ab). Colourless oil
1
À1
+
(30.8 mg, 81%). Eluant: petroleum ether (R
f
=0.50).
H
6
5
2
NMR (400 MHz, CDCl ) d 7.03 (dt, J=15.5, 6.9 Hz, 1H),
3
Calcd: 198.9658; Found: 198.9664.
6
.16 (d, J=15.6 Hz, 1H), 5.87 (d, J=50.3 Hz, 2H), 2.30–2.20
S-(fluoromethyl) decanethioate (3w). Colourless oil
33.6 mg, 76%). Eluant: petroleum ether (R =0.50).
NMR (400 MHz, CDCl ) d 5.80 (d, J=50.3 Hz, 2H), 2.73–
.29 (m, 2H), 1.76–1.62 (m, 2H), 1.38–1.07 (m, 12H), 0.88 (t,
(td, J=8.0, 1.1 Hz, 2H), 1.57–1.44 (m, 2H), 1.40–1.28 (m,
1
19
(
H
4H), 0.90 (t, J=6.9 Hz, 3H) ppm; F NMR (375 MHz,
f
13
CDCl ) d À191.76 (t, J=50.4 Hz, 1F) ppm; C NMR
3
3
2
(100 MHz, CDCl ) d 186.0 (d, J=1.6 Hz), 149.4, 128.1, 80.6
3
1
9
J=6.8 Hz, 3H) ppm; F NMR (375 MHz, CDCl ) d À192.16
(d, J=214.2 Hz), 32.5, 31.4, 27.6, 22.5, 14.0 ppm. IR (KBr):
n=3377, 2964, 2929, 2862, 1961, 1687, 1632, 1462, 1319, 1155,
3
1
3
(t, J=50.3 Hz, 1F) ppm; C NMR (100 MHz, CDCl ) d 195.8
3
À1
(d, J=1.7 Hz), 80.9 (d, J=213.9 Hz), 44.5, 31.9, 29.4, 29.29,
29.27, 28.9, 25.2, 22.7, 14.2 ppm. IR (KBr): n=3413, 2926,
857, 1969, 1718, 1462, 1321, 1126, 993, 914, 737 cm . HRMS
ESI) for C H FOSNa (M+Na ): Calcd: 243.1189; Found:
989, 798, 737, 640 cm . HRMS (ESI) for C H FOSNa (M+
9
15
+
Na ): Calcd: 213.0720; Found: 213.0727.
À1
2
(
+
S-(fluoromethyl) (E)-non-2-enethioate (3ac). Colourless oil
11 21
1
(
33.6 mg, 82%). Eluant: petroleum ether (R =0.50). H
f
243.1200.
Adv. Synth. Catal. 2018, 360, 1–10
7
ꢀ 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
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