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doi.org/10.1002/ejoc.202000598
EurJOC
European Journal of Organic Chemistry
Finally, after removal of the solvent, the reaction mixture was puri-
fied by flash column chromatography in hexane/ether (5:1).
Ethyl (S,E)-5-(1-(tert-butylsulfonyl)-2-(p-tolyl)-1,2,3,6-tetrahy-
dropyridin-4-yl)pent-4-enoate (7f). According to general proce-
dure VII, 7f was obtained as a white solid (23 mg, 35 % yield). M.p.
(S,E)-1-(tert-Butylsulfonyl)-4-styryl-2-(p-tolyl)-1,2,3,6-tetrahy-
dropyridine (7a). According to general procedure VII, 7a was ob-
tained as a colorless oil (40 mg, 65 % yield). [α]2D5 = +116.6 (c 1.0,
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74–75 °C; [α]2D5 = +66.9 (c 1.0, CHCl3); H NMR (300 MHz, CDCl3) δ
7.28 (d, J = 8.1 Hz, 2H), 7.10 (d, J = 8.0 Hz, 2H), 6.16 (d, J = 15.7 Hz,
1H), 5.80–5.67 (m, 1H), 5.57 (bs, 1H), 5.21 (bs, 1H), 4.15 (q, J = 7.1 Hz,
2H), 4.00 (dd, J = 19.0, 4.3 Hz, 1H), 3.48 (d, J = 19.6 Hz, 1H), 2.79
(bs, 2H), 2.53–2.39 (m, 4H), 2.31 (s, 3H), 1.41 (s, 9H), 1.26 (t, J =
7.1 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ = 173.1, 137.3, 136.2, 133.3,
132.7, 129.2, 127.6, 126.8, 123.4, 61.7, 60.5, 54.1, 42.9, 34.2, 28.2,
28.0, 24.8, 21.2, 14.4. HRMS (ESI): m/z calcd. for C23H39N2O4S [M +
NH4+]: 439.2480, found 439.2469.
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CHCl3); H NMR (300 MHz, CDCl3) δ 7.38–7.14 (m, 7H), 7.02 (d, J =
8.0 Hz, 2H), 6.77 (d, J = 16.2 Hz, 1H), 6.54 (d, J = 16.2 Hz, 1H), 5.71
(bs, 1H), 5.19 (bs, 1H), 3.99 (dd, J = 19.4, 4.3 Hz, 1H), 3.47 (dd, J =
19.4, 1.6 Hz, 1H), 2.89 (bs, 2H), 2.22 (s, 3H), 1.34 (s, 9H); 13C NMR
(75 MHz, CDCl3) δ = 137.8, 137.6, 136.5, 134.1, 130.7, 129.7, 129.3,
128.1 (d, J = 13.7 Hz), 127.5, 127.0, 126.1, 62.2, 54.6, 43.6, 28.4,
25.2, 21.6, 1.6. HRMS (ESI): m/z calcd. for C24H35N2O2S [M + NH4+]:
415.2250, found 415.2257.
(S,E)-4-(5-Bromopent-1-en-1-yl)-1-(tert-butylsulfonyl)-2-(p-
tolyl)-1,2,3,6-tetrahydropyridine (7g). According to general pro-
cedure VII, 7g was obtained as a colorless oil (25 mg, 36 % yield).
(S,E)-1-(tert-Butylsulfonyl)-4-(4-methylstyryl)-2-(p-tolyl)-1,2,3,6-
tetrahydropyridine (7b). According to general procedure VII, 7b
was obtained as a colorless oil (32 mg, 59 % yield). [α]2D5 = +128.9.
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[α]2D5 = +77.4 (c 1.0, CHCl3); H NMR (300 MHz, CDCl3) δ 7.29 (d, J =
8.1 Hz, 2H), 7.11 (d, J = 8.0 Hz, 2H), 6.18 (d, J = 15.8 Hz, 1H), 5.76–
5.62 (m, 1H), 5.58 (br, 1H), 5.22 (br, 1H), 4.01 (dd, J = 19.1, 4.3 Hz,
1H), 3.54–3.41 (m, 3H), 2.80 (br, 2H), 2.37–2.27 (m, 5H), 2.00 (m, 2H),
1.41 (s, 9H). 13C NMR (75 MHz, CDCl3) δ = 137.4, 136.2, 133.3, 133.0,
129.3, 127.6, 126.8, 123.3, 61.8, 54.2, 42.9, 33.3, 32.4, 31.2, 28.0, 24.8,
21.2. HRMS (ESI): m/z calcd. for C21H34BrN2O4S [M + NH4+]: 457.1526,
found 457.1519.
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(c 1.0, CHCl3); H NMR (300 MHz, CDCl3) δ 7.34 (dd, J = 8.1, 1.7 Hz,
4H), 7.14 (dd, J = 11.1, 8.0 Hz, 4H), 6.83 (d, J = 16.2 Hz, 1H), 6.61 (d,
J = 16.3 Hz, 1H), 5.78 (bs, 1H), 5.29 (bs, 1H), 4.08 (dd, J = 19.4, 4.4 Hz,
1H), 3.56 (dd, J = 19.6, 2.3 Hz, 1H), 2.98 (bs, 2H), 2.36 (s, 3H), 2.32
(s, 3H), 1.44 (s, 9H); 13C NMR (75 MHz, CDCl3) δ = 137.7, 137.4, 136.1,
134.3, 133.8, 129.6, 129.4, 129.3, 127.6, 127.0, 126.4, 125.0, 61.8, 54.2,
43.2, 28.0, 24.8, 21.4, 21.2. HRMS (ESI): m/z calcd. for C25H37N2O2S
[M + NH4+]: 429.2418, found 429.2414.
(S,E)-1-(tert-Butylsulfonyl)-4-(oct-1-en-1-yl)-2-(p-tolyl)-1,2,3,6-
tetrahydropyridine (7h). According to general procedure VII, 7h
was obtained as a colorless oil (20 mg, 32 % yield). [α]2D5 = +77.6 (c
1.0, CHCl3); 1H NMR (300 MHz, CDCl3) δ 7.30 (d, J = 8.1 Hz, 2H), 7.11
(d, J = 8.0 Hz, 2H), 6.12 (d, J = 15.7 Hz, 1H), 5.83–5.66 (m, 1H), 5.55
(bs, 1H), 5.21 (t, J = 3.7 Hz, 1H), 3.99 (dd, J = 18.9, 4.3 Hz, 1H), 3.48
(d, J = 18.6 Hz, 1H), 2.81 (bs, 2H), 2.31 (s, 3H), 2.22–2.08 (m, 2H),
1.41 (s, J = 9.1 Hz, 9H), 1.40–1.24 (m, 8H), 0.90 (t, J = 6.8 Hz, 3H);
13C NMR (75 MHz, CDCl3) δ = 137.2, 136.3, 133.6, 131.5, 129.5, 129.2,
127.6, 122.2, 61.7, 54.2, 42.9, 33.0, 31.9, 29.5, 29.1, 28.0, 24.8, 22.8,
21.2, 14.2. HRMS (ESI): m/z calcd. for C24H41N2O2S [M + NH4+]:
421.2883, found 421.2883.
(S,E)-1-(tert-Butylsulfonyl)-4-(4-chlorostyryl)-2-(p-tolyl)-1,2,3,6-
tetrahydropyridine (7c). According to general procedure VII, 7c
was obtained as a white solid (22 mg, 33 % yield). M.p. 139–140 °C;
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[α]2D5 = +102.8 (c 1.0, CHCl3); H NMR (300 MHz, CDCl3) δ 7.40–7.28
(m,6), 7.12 (d, J = 8.0 Hz, 2H), 6.83 (d, J = 16.2 Hz, 1H), 6.57 (d, J =
16.2 Hz, 1H), 5.82 (bs, 1H), 5.29 (bs, 1H), 4.09 (dd, J = 19.1, 4.4 Hz,
1H), 3.56 (d, J = 19.5 Hz, 1H), 2.96 (bs, 2H), 2.31 (s, 3H), 1.43 (s, 9H);
13C NMR (75 MHz, CDCl3) δ = 137.4, 135.9, 135.6, 133.4, 133.2, 130.8,
129.2, 128.9, 127.6, 127.4, 126.2, 125.7, 61.7, 54.0, 43.1, 27.8, 24.7,
21.0. HRMS (ESI): m/z calcd. for C24H34ClN2O2S [M + NH4+]: 449.1863,
found 449.1868.
(S,E)-1-(tert-Butylsulfonyl)-2-(p-tolyl)-4-(3-(trimethylsilyl)prop-
1-en-1-yl)-1,2,3,6-tetrahydropyridine (7i). According to general
procedure VII, 7i was obtained as a colorless oil (45 mg, 33 % yield);
(S,E)-1-(tert-Butylsulfonyl)-4-(4-fluorostyryl)-2-(p-tolyl)-1,2,3,6-
tetrahydropyridine (7d). According to general procedure VII, 7d
was obtained as a white solid (30 mg, 47 % yield). mp 110–111 °C;
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[α]2D5 = +53.1 (c 1.0, CHCl3); H NMR (300 MHz, CDCl3) δ 7.30 (d, J =
1
[α]2D5 = +110.3 (c 1.0, CHCl3); H NMR (300 MHz, CDCl3) δ 7.41 (dd,
8.0 Hz, 2H), 7.11 (d, J = 8.0 Hz, 2H), 5.99 (d, J = 15.6 Hz, 1H), 5.82–
5.71 (m, 1H), 5.45 (s, 1H), 5.20 (t, J = 3.7 Hz, 1H), 3.99 (dd, J = 18.8,
4.2 Hz, 1H), 3.48 (d, J = 18.8 Hz, 1H), 2.79 (s, 2H), 2.31 (s, 3H), 1.60
(d, J = 8.1 Hz, 2H), 1.42 (s, 9H), 0.04 (s, 9H); 13C NMR (75 MHz, CDCl3)
δ = 139.0, 138.1, 135.4, 132.0, 130.9, 129.4, 129.3, 127.7, 122.4, 63.5,
55.9, 44.7, 29.8, 26.5, 25.5, 22.9, 0.00. HRMS (ESI): m/z calcd. for
J = 8.7, 5.4 Hz, 2H), 7.33 (d, J = 8.1 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H),
7.03 (t, J = 8.7 Hz, 2H), 6.78 (d, J = 16.2 Hz, 1H), 6.59 (d, J = 16.2 Hz,
1H), 5.80 (bs, 1H), 5.29 (bs, 1H), 4.09 (dd, J = 19.4, 4.3 Hz, 1H), 3.56
(dd, J = 19.5, 2.0 Hz, 1H), 2.96 (bs, 2H), 2.32 (s, 3H), 1.43 (s, 9H); 13C
NMR (75 MHz, CDCl3) δ = 162.4 (d, J = 247.3 Hz), 137.4, 136.0, 133.6,
133.4 (d, J = 3.4 Hz), 130.1 (d, J = 2.2 Hz), 129.3, 128.1 (s, J = 7.9 Hz),
128.0, 127.6, 125.8 (d, J = 11.4 Hz), 115.8 (d, J = 21.7 Hz), 61.8, 54.1,
C
22H39N2O2SSi [M + NH4+]: 423.2158, found 423.2163.
43.2, 28.0, 24.8, 21.2; 19F NMR (282 MHz, CDCl3) δ –14.14 (t, J = (S,E)-1-(tert-Butylsulfonyl)-2-phenyl-4-styryl-1,2,3,6-tetrahydro-
9.0 Hz). HRMS (ESI): m/z calcd. for C24H34FN2O2S [M + NH4+]:
433.2172, found 433.2163.
pyridine (7j). According to general procedure VII, 7j was obtained
as a white solid (43 mg, 68 % yield). M.p. 129–131 °C; [α]2D5 = +134.7
1
(c 1.0, CHCl3); H NMR (300 MHz, CDCl3) δ 7.49–7.25 (m, 10H), 6.88
(S,E)-4-(2-Bromostyryl)-1-(tert-butylsulfonyl)-2-(p-tolyl)-1,2,3,6-
tetrahydropyridine (7e). According to general procedure VII, 7e
was obtained as a white solid (17 mg, 23 % yield). M.p. 226–228 °C;
[α]2D5 = +105.1 (c 1.0, CHCl3); 1H NMR (300 MHz, CDCl3) δ 7.59 (td,
J = 7.9, 1.3 Hz, 2H), 7.39–7.28 (m, 3H), 7.16–7.07 (m, 3H), 7.00 (d, J =
16.2 Hz, 1H), 6.79 (d, J = 16.2 Hz, 1H), 5.87 (bs, 1H), 5.30 (bs, 1H),
4.10 (dd, J = 19.4, 4.3 Hz, 1H), 3.58 (dd, J = 19.6, 1.9 Hz, 1H), 3.03
(bs, 2H), 2.32 (s, 3H), 1.44 (s, 9H); 13C NMR (75 MHz, CDCl3) δ =
(d, J = 16.3 Hz, 1H), 6.65 (d, J = 16.3 Hz, 1H), 5.82 (bs, 1H), 5.33 (bs,
1H), 4.10 (dd, J = 19.5, 4.4 Hz, 1H), 3.57 (dd, J = 19.5, 2.2 Hz, 1H),
3.01 (bs, 2H), 1.45 (s, 9H); 13C NMR (75 MHz, CDCl3) δ = 139.1, 137.1,
133.6, 130.2, 128.8, 128.6, 127.8, 127.7, 127.7, 127.1, 126.5, 125.6,
61.8, 54.3, 43.3, 27.8, 24.8. HRMS (ESI): m/z calcd. for C23H33N2O2S
[M + NH4+]: 401.2098, found 401.2101.
(S,E)-1-(tert-Butylsulfonyl)-4-(4-methylstyryl)-2-phenyl-1,2,3,6-
137.5, 136.9, 136.0, 133.9, 133.3, 132.9, 129.4, 129.0, 127.7, 127.6, tetrahydropyridine (7k). According to general procedure VII, 7k
126.8, 126.6, 125.8, 124.3, 61.9, 54.2, 43.3, 28.0, 24.8, 21.2. HRMS
(ESI): m/z calcd. for C24H34BrN2O2S [M + NH4+]: 493.1354, found
493.1362.
was obtained as a white solid (20 mg, 39 % yield). M.p. 66–67 °C;
[α]2D5 = +134.9 (c 1.0, CHCl3); 1H NMR (300 MHz, CDCl3) δ 7.38 (d,
J = 7.2 Hz, 2H), 7.31–7.17 (m, 5H), 7.08 (d, J = 8.0 Hz, 2H), 6.76 (d,
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