R. Li et al. / Tetrahedron 72 (2016) 5707e5712
5711
43.03, 14.32; HRMS: C11H18NO3S2 Calcd for [MþH]þ 276.0728,
13C NMR (100 MHz, CDCl3)
d
191.68, 171.38, 134.39, 133.65, 61.85,
Found 276.0727.
55.42, 43.68, 31.39, 25.50, 24.74, 14.24; HRMS: C13H22NO2S2 Calcd
for [MþH]þ 288.1092, Found 288.1086.
4.2.3. Ethyl 3-[(pyrrolidine-1-carbonothioyl)thio]but-3-enoate
(3c). 87% yield, brown oil; 1H NMR (400 MHz, CDCl3)
d
5.93 (s,
4.2.11. Ethyl 3-[(benzylcarbamothioyl)thio]but-3-enoate (3k). 95%
1H), 5.76 (s, 1H), 4.16 (q, J¼7.2 Hz, 2H), 3.89 (t, J¼6.8 Hz, 2H), 3.67 (s,
yield, white solid, mp¼56e58 ꢀC; 1H NMR (400 MHz, CDCl3)
d 8.37
2H), 3.64 (t, J¼6.8 Hz, 2H), 2.14e2.05 (m, 2H), 2.02e1.95 (m, 2H),
(s, 1H), 7.38e7.31 (m, 5H), 5.93 (d, J¼28.4 Hz, 2H), 4.90 (d, J¼5.6 Hz,
1.26 (t, J¼7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d 190.97, 170.56,
2H), 4.10 (q, J¼7.2 Hz, 2H), 3.40 (s, 2H), 1.23 (t, J¼7.2 Hz, 3H); 13C
134.42, 132.02, 60.96, 54.89, 51.26, 43.02, 26.43, 24.52, 14.29;
NMR (100 MHz, CDCl3) d 193.83, 171.19, 136.16, 134.53, 133.52,
HRMS: C11H18NO2S2 Calcd for [MþH]þ 260.0779, Found 260.0774.
128.93, 128.32, 128.11, 61.84, 50.71, 43.75, 14.21; HRMS:
C
14H18NO2S2 Calcd for [MþH]þ 296.0779, Found 296.0776.
4.2.4. Ethyl 3-[(azepane-1-carbonothioyl)thio]but-3-enoate
(3d). 80% yield, yellow oil; 1H NMR (400 MHz, CDCl3)
d
5.92 (s,
4.2.12. Ethyl 3-[[(1-phenylethyl)carbamothioyl]thio]but-3-enoate
(3l). 81% yield, brown oil; 1H NMR (400 MHz, CDCl3)
8.54 (d,
1H), 5.75 (s, 1H), 4.23e4.06 (m, 4H), 3.86 (t, J¼6.0 Hz, 2H), 3.65 (s,
d
2H), 1.86 (d, J¼3.6 Hz, 4H), 1.65e1.56 (m, 4H), 1.26 (t, J¼7.2 Hz, 3H);
J¼7.6 Hz,1H), 7.36e7.28 (m, 5H), 5.99 (s, 1H), 5.89 (s, 1H), 5.76e5.69
13C NMR (100 MHz, CDCl3)
d 194.34, 170.63, 134.77, 131.75, 60.96,
(m, 1H), 4.19 (qd, J¼7.2, 1.6 Hz, 2H), 3.40 (s, 2H), 1.61 (d, J¼6.8 Hz,
55.44, 53.66, 43.11, 27.64, 26.81, 26.68, 26.31, 14.31; HRMS:
3H), 1.27 (t, J¼7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d 192.35,
C
13H22NO2S2 Calcd for [MþH]þ 288.1092, Found 288.1090.
171.54, 141.50, 134.72, 133.49, 128.78, 127.75, 126.61, 61.90, 55.68,
43.73, 20.69, 14.23; HRMS:
310.0935, Found 310.0930.
C
15H20NO2S2 Calcd for [MþH]þ
4.2.5. Ethyl 3-[(diethylcarbamothioyl)thio]but-3-enoate (3e). 84%
yield, yellow oil; 1H NMR (400 MHz, CDCl3)
5.92 (s, 1H), 5.75 (s,
d
1H), 4.16 (q, J¼7.2 Hz, 2H), 4.00 (q, J¼7.2 Hz, 2H), 3.72 (q, J¼7.2 Hz,
4.2.13. Ethyl 3-[[(thiophen-2-ylmethyl)carbamothioyl]thio]but-3-
2H), 3.64 (s, 2H), 1.36e1.19 (m, 9H); 13C NMR (100 MHz, CDCl3)
enoate (3m). 90% yield, yellow solid, mp¼64e65 ꢀC; 1H NMR
d
193.59, 170.61, 134.67, 131.84, 60.95, 49.31, 47.61, 43.08, 14.28,
(400 MHz, CDCl3)
d
8.41 (s, 1H), 7.28e7.24 (m, 1H), 7.08 (dd, J¼3.6,
12.73, 11.69; HRMS: C11H20NO2S2 Calcd for [MþH]þ 262.0935,
0.8 Hz,1H), 6.98 (dd, J¼5.2, 3.6 Hz,1H), 5.99 (s,1H), 5.90 (s,1H), 5.06
Found 262.0926.
(d, J¼5.2 Hz, 2H), 4.12 (q, J¼7.2 Hz, 2H), 3.40 (s, 2H), 1.25 (t, J¼7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3)
d 193.68, 171.24, 138.12, 134.72,
4.2.6. Ethyl 3-[(benzyl(methyl)carbamothioyl)thio]but-3-enoate
133.35, 127.35, 127.06, 125.94, 61.87, 45.15, 43.67, 14.21; HRMS:
C
(3f). 80% yield, brown oil; 1H NMR (400 MHz, CDCl3)
d
7.48e7.15
12H16NO2S3 Calcd for [MþH]þ 302.0343, Found 302.0342.
(m, 5H), 5.95 (d, J¼5.2 Hz, 1H), 5.78 (d, J¼8.8 Hz, 1H), 5.32 (s, 1H),
4.96 (s, 1H), 4.24e4.06 (m, 2H), 3.68 (d, J¼12.0 Hz, 2H), 3.55e3.11
4.2.14. Ethyl 3-[[(furan-2-ylmethyl)carbamothioyl]thio]but-3-enoate
(m, 3H), 1.27 (t, J¼7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d
196.93,
(3n). 92% yield, yellow solid, mp¼60e62 ꢀC; 1H NMR (400 MHz,
170.56, 135.49, 134.70, 132.14, 128.88, 127.95, 127.25, 61.00, 59.12,
CDCl3) d 8.35 (s, 1H), 7.39 (s, 1H), 6.35 (s, 2H), 6.00 (s, 1H), 5.91 (s,
42.91, 39.45, 14.29; HRMS:
310.0935, Found 310.0924.
C
15H20NO2S2 Calcd for [MþH]þ
1H), 4.88 (d, J¼5.2 Hz, 2H), 4.14 (q, J¼7.2 Hz, 2H), 3.42 (s, 2H),1.26 (t,
J¼7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d 193.91, 171.15, 149.11,
142.74, 134.59, 133.35, 110.69, 109.03, 61.83, 43.60, 43.46, 14.20;
4.2.7. Ethyl 3-[(propylcarbamothioyl)thio]but-3-enoate (3g). 85%
HRMS: C12H16NO3S2 Calcd for [MþH]þ 286.0572, Found 286.0569.
yield, yellow solid, mp¼64e66 ꢀC; 1H NMR (400 MHz, CDCl3)
d 8.29
(s, 1H), 6.02 (s, 1H), 5.94 (s, 1H), 4.20 (q, J¼7.2 Hz, 2H), 3.66 (dd,
J¼12.4, 7.2 Hz, 2H), 3.43 (s, 2H), 1.71 (dd, J¼14.6, 7.2 Hz, 3H), 1.29 (t,
J¼7.2 Hz, 3H), 0.98 (t, J¼7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3)
4.2.15. Benzyl 3-[(piperidine-1-carbonothioyl)thio]but-3-enoate
(3o). 82% yield, yellow oil; 1H NMR (400 MHz, CDCl3)
d
7.35e7.31
(m, 5H), 5.92 (s, 1H), 5.75 (s, 1H), 5.14 (s, 2H), 4.21 (s, 2H), 3.79 (s,
2H), 3.71 (s, 2H), 1.67 (s, 6H); 13C NMR (100 MHz, CDCl3)
193.24,
d
193.27, 171.57, 134.62, 133.57, 61.90, 48.67, 43.75, 21.43, 14.22,
d
11.52; HRMS: C10H18NO2S2 Calcd for [MþH]þ 248.0779, Found
170.29, 135.77, 134.32, 131.92, 128.50, 128.20, 128.16, 66.59, 52.34,
50.04, 43.00, 26.01, 25.33, 24.07; HRMS: C17H22NO2S2 Calcd for
[MþH]þ 336.1092, Found 336.1088.
248.0777.
4.2.8. Ethyl 3-[(isopropylcarbamothioyl)thio]but-3-enoate (3h). 88%
yield, yellow solid, mp¼60e61 ꢀC; 1H NMR (400 MHz, CDCl3)
d
8.09
4.2.16. Benzyl 3-[(benzylcarbamothioyl)thio]but-3-enoate (3p). 82%
(s, 1H), 6.01 (s, 1H), 5.92 (s, 1H), 4.78e4.50 (m,1H), 4.20 (q, J¼7.2 Hz,
yield, yellow oil; 1H NMR (400 MHz, CDCl3)
d 8.29 (s, 1H), 7.37e7.34
2H), 3.41 (d, J¼0.8 Hz, 2H), 1.40e1.14 (m, 9H); 13C NMR (100 MHz,
(m, 5H), 7.33e7.29 (m, 5H), 5.96 (s, 1H), 5.88 (s, 1H), 5.07 (s, 2H),
CDCl3)
d 191.84, 171.54, 134.65, 133.49, 61.88, 48.71, 43.72, 21.27,
4.85 (d, J¼5.6 Hz, 2H), 3.46 (s, 2H).; 13C NMR (100 MHz, CDCl3)
14.25; HRMS: C10H18NO2S2 Calcd for [MþH]þ 248.0779, Found
d 193.64, 170.95, 136.07, 135.18, 134.63, 133.24, 128.90, 128.78,
248.0772.
128.68, 128.49, 128.30, 128.08, 67.54, 50.65, 43.63; HRMS:
C
19H20NO2S2 Calcd for [MþH]þ 358.0935, Found 358.0920.
4.2.9. Ethyl
3-[(allylcarbamothioyl)thio]but-3-enoate
(3i). 91%
yield, brown oil; 1H NMR (400 MHz, CDCl3)
d
8.25 (s, 1H), 6.03 (s,
4.2.17. Benzyl 3-[(propylcarbamothioyl)thio]but-3-enoate (3q). 81%
yield, yellow oil; 1H NMR (400 MHz, CDCl3)
8.15 (s, 1H), 7.39e7.34
1H), 5.99e5.85 (m, 2H), 5.32e5.23 (m, 2H), 4.34 (t, J¼5.6 Hz, 2H),
d
4.19 (q, J¼7.2 Hz, 2H), 3.43 (s, 2H), 1.29 (t, J¼7.2 Hz, 3H); 13C NMR
(m, 5H), 6.01 (s, 1H), 5.92 (s, 1H), 5.16 (s, 2H), 3.60 (dd, J¼14.4,
(100 MHz, CDCl3)
d 193.76, 171.38, 134.72, 133.46, 131.77, 118.41,
5.6 Hz, 2H), 3.48 (s, 2H), 1.66 (dd, J¼14.8, 7.2 Hz, 2H), 0.95 (t,
61.92, 49.10, 43.77, 14.24; HRMS: C10H16NO2S2 Calcd for [MþH]þ
J¼7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d 193.06, 171.20, 135.10,
246.0622, Found 246.0621.
134.57, 133.36, 128.76, 128.67, 128.43, 67.42, 48.60, 43.64, 21.37,
11.48; HRMS: C15H20NO2S2 Calcd for [MþH]þ 310.0935 Found
310.0934.
4.2.10. Ethyl 3-[(cyclohexylcarbamothioyl)thio]but-3-enoate
(3j). 88% yield, pale yellow oil; 1H NMR (400 MHz, CDCl3)
d 8.11
(s, 1H), 6.01 (s, 1H), 5.91 (s, 1H), 4.37e4.34 (m, 1H), 4.20 (q, J¼7.2 Hz,
2H), 3.40 (d, J¼0.8 Hz, 2H), 2.04 (dd, J¼12.0, 3.2 Hz, 2H), 1.78e1.72
(m, 2H), 1.62e1.66 (m, 2H), 1.36e1.43 (m, 2H), 1.32e1.27 (m, 5H);
4.2.18. (E)-Ethyl 3-[(piperidine-1-carbonothioyl)thio]pent-3-enoate
(3r). 77% yield, yellow solid, mp¼56e57 ꢀC; 1H NMR (400 MHz,
CDCl3)
d
6.16 (q, J¼6.8 Hz, 1H), 4.15 (s, 2H), 4.05 (dd, J¼14.0, 6.8 Hz,