The Journal of Organic Chemistry
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cm−1; HRMS (ESI) calcd for C33H35NO6S2Na (M+ + Na) 628.1804,
found 628.1815.
4H), 2.75 (dd, 1H, J = 18.2, 4.8 Hz), 3.01−3.17 (m, 2H), 4.20 (dd,
1H, J = 14.0, 5.6 Hz), 4.50 (d, 1H, J = 7.0 Hz), 6.97−7.15 (m, 9H),
7.30 (t, 1H, J = 7.2 Hz), 7.44 (m, 2H, J = 8.0 Hz), 7.99 (d, 2H, J = 8.1
Hz); 13C NMR (CDCl3, 100 MHz) δ 11.0, 21.7, 25.3, 30.3, 30.3, 42.7,
44.1, 58.3, 127.5, 127.8, 128.0, 128.1, 128.8, 128.9, 130.0, 133.0, 135.4,
136.2, 137.8, 138.3, 140.3, 143.5, 198.2, 205.9; IR (NaCl, neat) ν 1717,
1657 cm−1; HRMS (ESI) calcd for C30H32NO4S (M+ + H) 502.2052,
found 502.2047.
(3S,4S)-4-(N-Allyl-4-methylphenylsulfonamido)-6-(methylsulfon-
yl)-1,3-diphenylhex-1-yn-3-yl hexanoate (1t): yield 55%; 0.350 g;
yellow oil; [α]23D −74.0 (c 1.0, CHCl3); 1H NMR (CDCl3, 400 MHz)
δ 0.87 (t, 3H, J = 6.8 Hz), 1.28−1.33 (m, 4H), 1.58−1.65 (m, 2H),
2.28 (s, 3H), 2.37 (td, 2H, J = 7.5, 2.3 Hz), 2.61−2.67 (m, 2H), 2.91
(s, 3H), 3.07−3.15 (m, 1H), 3.21−3.29 (m, 1H), 3.98 (d, 1H, J = 15.6
Hz), 4.17 (d, 1H, J = 16.6, 8.2 Hz), 4.80 (s, 1H), 4.96 (d, 1H, J = 10.2
Hz), 5.06 (d, 1H, J = 17.2 Hz), 5.70−5.76 (m, 1H), 6.98 (s, 4H),
7.28−7.44 (m, 8H), 7.59−7.60 (m, 2H); 13C NMR (CDCl3, 100
MHz) δ 13.9, 20.6, 21.5, 22.3, 24.4, 31.2, 34.8, 41.3, 47.0, 52.1, 64.5,
81.1, 85.3, 91.3, 118.1, 121.6, 126.4, 128.1, 128.4, 128.5, 128.7, 129.2,
129.3, 131.9, 134.7, 136.2, 139.3, 143.6, 170.0; IR (NaCl, neat) ν 3024,
2229, 1755, 1317, 1217, 1153 cm−1; HRMS (ESI) calcd for
C35H41NO6S2Na (M+ + Na) 658.2273, found 658.2266.
1-((3R,6S)-4-Benzoyl-6-isopropyl-5-phenyl-1-tosyl-1,2,3,6-tetra-
hydropyridin-3-yl)propan-2-one (2f): yield 73%; 0.075 g; colorless
1
solid; mp = 101−102 °C; [α]23 +187.5 (c 1.0, CHCl3); H NMR
D
(CDCl3, 400 MHz) δ 0.88 (d, 3H, J = 6.7 Hz), 0.92 (d, 3H, J = 7.0
Hz), 1.80−1.88 (m, 1H), 2.09 (s, 3H), 2.42 (dd, 1H, J = 18.3, 7.4 Hz),
2.49 (s, 3H), 2.81 (dd, 1H, J = 18.3, 4.8 Hz), 2.99 (m, 1H), 3.15 (dd,
1H, J = 14.8, 11.0 Hz), 4.26 (dd, 1H, J = 14.7, 6.4 Hz), 4.59 (d, 1H, J =
4.6 Hz), 7.00−7.16 (m, 9H), 7.30 (t, 1H, J = 7.2 Hz), 7.44 (m, 2H, J =
8.0 Hz), 8.00 (d, 2H, J = 8.2 Hz); 13C NMR (CDCl3, 100 MHz) δ
19.3, 20.6, 21.7, 29.8, 30.3, 31.9, 44.7, 44.9, 61.0, 127.7, 127.7, 128.0,
128.1, 128.8, 128.9, 130.0, 132.9, 136.0, 137.0, 138.1, 138.6, 139.0,
143.5, 198.4, 205.8; IR (NaCl, neat) ν 1719, 1655 cm−1; HRMS (ESI)
calcd for C31H34NO4S (M+ + H) 516.2209, found 516.2200.
1-((3R,6S)-4-Benzoyl-6-benzyl-5-phenyl-1-tosyl-1,2,3,6-tetrahy-
dropyridin-3-yl)propan-2-one (2a): yield 75%; 0.085 g; colorless
1
solid; mp = 143−145 °C; [α]23 +103.4 (c 1.0, CHCl3); H NMR
D
(CDCl3, 400 MHz) δ 2.13 (s, 3H), 2.41 (s, 3H), 2.48 (dd, 1H, J =
18.2, 7.1 Hz), 2.74 (dd, 1H, J = 18.2, 4.6 Hz), 2.85−2.87 (m, 2H), 3.08
(dd, 1H, J = 14.4, 11.0 Hz), 3.19−3.26 (m, 1H), 3.92 (dd, 1H, J =
14.4, 6.2 Hz), 4.99 (t, 1H, J = 6.5 Hz), 6.98−7.01 (m, 2H), 7.07−7.20
(m, 12H), 7.33−7.48 (m, 5H); 13C NMR (CDCl3, 100 MHz) δ 21.6,
30.4, 30.8, 38.1, 42.5, 44.0, 58.1, 126.4, 127.6, 128.0, 128.2, 128.3,
129.0, 129.2, 129.4, 129.6, 133.1, 136.1, 136.4, 136.9, 137.6, 137.7,
139.6, 143.2, 198.3, 206.0; IR (NaCl, neat) ν 3021, 1717, 1659, 1597,
1215 cm−1; HRMS (ESI) calcd for C35H34NO4S (M+ + H) 564.2209,
found 564.2218.
1-((3R,6S)-4-Benzoyl-6-isobutyl-5-phenyl-1-tosyl-1,2,3,6-tetrahy-
dropyridin-3-yl)propan-2-one (2g): yield 60%; 0.064 g; colorless
1
solid; mp = 137−138 °C; [α]23 +174.4 (c 1.0, CHCl3); H NMR
D
(CDCl3, 400 MHz) δ 0.70 (d, 3H, J = 6.4 Hz), 0.81 (d, 3H, J = 6.6
Hz), 1.05−1.12 (m, 1H), 1.61−1.75 (m, 2H), 2.10 (s, 3H), 2.43−2.48
(m, 4H), 2.77 (dd, 1H, J = 18.2, 4.6 Hz), 3.07−3.20 (m, 2H), 4.11−
4.17 (m, 1H), 4.67 (d, 1H, J = 10.3 Hz), 6.98−7.10 (m, 7H), 7.17 (d,
2H, J = 7.4 Hz), 7.29 (t, 1H, J = 7.3 Hz), 7.44 (m, 2H, J = 8.1 Hz),
7.99 (d, 2H, J = 8.1 Hz); 13C NMR (CDCl3, 100 MHz) δ 20.9, 21.7,
23.6, 24.4, 30.1, 30.3, 41.3, 42.5, 44.2, 127.7, 127.8, 128.0, 128.1, 128.8,
129.0, 130.0, 132.9, 135.2, 136.2, 137.8, 138.0, 140.6, 143.6, 198.3,
205.9; IR (NaCl, neat) ν 1717, 1657 cm−1; HRMS (ESI) calcd for
C32H36NO4S (M+ + H) 530.2365, found 530.2358.
1-((3R,6S)-6-Benzyl-4-(4-bromobenzoyl)-5-phenyl-1-tosyl-1,2,3,6-
tetrahydropyridin-3-yl)propan-2-one (2b): yield 66%; 0.085 g; yellow
solid; mp =74−76 °C; [α]23D +62.7 (c 1.0, CHCl3); 1H NMR (CDCl3,
400 MHz) δ 2.13 (s, 3H), 2.41 (s, 3H), 2.48 (dd, 1H, J = 18.2, 6.4
Hz), 2.72−2.89 (m, 3H), 3.10 (dd, 1H, J = 14.2, 11.0 Hz), 3.20−3.26
(m, 1H), 3.91 (dd, 1H, J = 14.4, 6.2 Hz), 4.93−4.96 (m, 1H), 6.95−
6.97 (m, 2H), 7.09−7.17 (m, 10H), 7.31−7.37 (m, 4H), 7.43 (d, 2H, J
= 8.2 Hz); 13C NMR (CDCl3, 100 MHz) δ 21.6, 30.4, 30.7, 38.0, 42.5,
43.9, 58.1, 126.4, 127.6, 128.3, 128.3, 128.5, 128.9, 129.3, 129.6, 130.6,
131.6, 134.9, 136.0, 136.6, 137.5, 137.5, 139.9, 143.3, 197.4, 206.0; IR
(NaCl, neat) ν 1717, 1663 cm−1; HRMS (ESI) calcd for
C35H33NO4S79Br (M+ + H) 642.1314, found 642.1323.
1-((3R,6S)-6-Benzyl-4-(4-methylbenzoyl)-5-phenyl-1-tosyl-1,2,3,6-
tetrahydropyridin-3-yl)propan-2-one (2c): yield 74%; 0.086 g; pale
yellow solid; mp = 80−82 °C; [α]23D +91.5 (c 1.0, CHCl3); 1H NMR
(CDCl3, 400 MHz) δ 2.10 (s, 3H), 2.27 (s, 3H), 2.40−2.46 (m, 4H),
2.72 (dd, 1H, J = 18.2, 4.6 Hz), 2.82−2.90 (m, 2H), 3.04 (dd, 1H, J =
14.4, 11.0 Hz), 3.16−3.23 (m, 2H), 3.93 (dd, 1H, J = 14.4, 6.3 Hz),
4.99 (t, 1H, J = 6.6 Hz), 6.98−7.01 (m, 4H), 7.08−7.21 (m, 10H),
7.40 (d, 2H, J = 8.0 Hz), 7.47 (d, 2H, J = 8.1 Hz); 13C NMR (CDCl3,
100 MHz) δ 21.6, 21.7, 30.4, 30.8, 38.1, 42.5, 44.1, 58.0, 126.4, 127.6,
128.0, 128.3, 129.0, 129.1, 129.4, 129.5, 129.6, 133.5, 136.6, 136.9,
137.6, 137.8, 138.9, 143.2, 144.1, 197.8, 206.0; IR (NaCl, neat) ν 1717,
1603 cm−1; HRMS (ESI) calcd for C36H36NO4S (M+ + H) 578.2365,
found 578.2375.
1-((3R,6S)-4-Benzoyl-6-benzyl-5-phenyl-1-tosyl-1,2,3,6-tetrahy-
dropyridin-3-yl)pentan-2-one (2h): yield 67%; 0.079 g; colorless
1
solid; mp = 147−148 °C; [α]23 +112.4 (c 1.0, CHCl3); H NMR
D
(CDCl3, 400 MHz) δ 0.88 (t, 3H, J = 7.4 Hz), 1.50−1.59 (m, 2H),
2.31−2.43 (m, 6H), 2.70 (dd, 1H, J = 18.0, 4.7 Hz), 2.83−2.90 (m,
2H), 3.04 (dd, 1H, J = 14.4, 11.0 Hz), 3.19−3.25 (m, 1H), 3.93 (dd,
1H, J = 14.5, 6.2 Hz), 4.98 (t, 1H, J = 6.5 Hz), 7.00−7.19 (m, 13H),
7.25−7.35 (m, 2H), 7.43−7.49 (m, 4H); 13C NMR (CDCl3, 100
MHz) δ 13.7, 17.1, 21.6, 30.8, 38.2, 42.7, 43.3, 45.0, 58.1, 126.4, 127.6,
128.0, 128.2, 128.3, 129.1, 129.2, 129.5, 129.6, 133.1, 136.1, 136.6,
137.0, 137.6, 137.7, 139.4, 143.2, 198.2, 208.3; IR (NaCl, neat) ν 3022,
1713, 1661, 1217 cm−1; HRMS (ESI) calcd for C37H38NO4S (M+ +
H) 592.2522, found 592.2528.
1-((3R,6S)-4-Benzoyl-6-benzyl-5-phenyl-1-tosyl-1,2,3,6-tetrahy-
dropyridin-3-yl)heptan-2-one (2i): yield 77%; 0.096 g; yellow oil;
1
[α]23 +89.5 (c 1.0, CHCl3); H NMR (CDCl3, 400 MHz) δ 0.88 (t,
D
3H, J = 7.2 Hz), 1.19−1.32 (m, 4H), 1.48−1.55 (m, 2H), 2.34−2.43
(m, 6H), 2.70 (dd, 1H, J = 18.0, 4.6 Hz), 2.85−2.90 (m, 2H), 3.03
(dd, 1H, J = 14.3, 11.0 Hz), 3.21−3.23 (m, 1H), 3.93 (dd, 1H, J =
14.6, 6.2 Hz), 4.98 (d, 1H, J = 6.4 Hz), 7.00−7.19 (m, 14H), 7.32−
7.35 (m, 1H), 7.43−7.49 (m, 4H); 13C NMR (CDCl3, 100 MHz) δ
13.9, 21.6, 22.4, 23.3, 30.8, 31.3, 38.2, 42.7, 43.1, 43.3, 58.1, 126.4,
127.6, 128.0, 128.2, 128.3, 129.1, 129.2, 129.5, 129.6, 129.6, 133.1,
136.1, 136.6, 137.0, 137.6, 137.7, 139.4, 143.2, 198.2, 208.4; IR (NaCl,
neat) ν 1713, 1661 cm−1; HRMS (ESI) calcd for C39H42NO4S (M+ +
H) 620.2835, found 620.2825.
1-((3R,6S)-6-Benzyl-5-phenyl-4-(thiophene-3-carbonyl)-1-tosyl-
1,2,3,6-tetrahydropyridin-3-yl)propan-2-one (2d): yield 53%; 0.061
1
g; yellow oil; [α]23 +71.4 (c 1.0, CHCl3); H NMR (CDCl3, 400
D
MHz) δ 2.15 (s, 3H), 2.40 (s, 3H), 2.51 (dd, 1H, J = 18.2, 7.2 Hz),
2.73−2.90 (m, 3H), 3.12 (dd, 1H, J = 14.0, 11.4 Hz), 3.26−3.27 (m,
1H), 3.97 (dd, 1H, J = 14.5, 6.4 Hz), 4.93 (t, 1H, J = 5.3 Hz), 6.95−
7.03 (m, 3H), 7.14−7.21 (m, 11H), 7.44 (d, 2H, J = 7.8 Hz), 7.59 (s,
1H); 13C NMR (CDCl3, 100 MHz) δ 21.6, 30.4, 30.8, 37.9, 42.4, 44.1,
58.1, 126.1, 126.3, 126.7, 127.6, 128.1, 128.3, 128.4, 128.9, 129.3,
129.7, 135.9, 136.7, 137.2, 137.6, 137.8, 139.2, 141.4, 143.4, 191.8,
206.1; IR (NaCl, neat) ν 1717, 1651 cm−1; HRMS (ESI) calcd for
C33H32NO4S2 (M+ + H) 570.1773, found 570.1774.
1-((3R,6S)-4-Benzoyl-6-ethyl-5-phenyl-1-tosyl-1,2,3,6-tetrahydro-
pyridin-3-yl)propan-2-one (2e): yield 61%; 0.061 g; colorless oil;
[α]23D +198.9 (c 1.0, CHCl3); 1H NMR (CDCl3, 400 MHz) δ 0.86 (t,
30H, J = 7.3 Hz), 1.48−1.62 (m, 1H), 2.10 (s, 3H), 2.42−2.49 (m,
1-((3R,6S)-4-Benzoyl-6-benzyl-5-phenyl-1-tosyl-1,2,3,6-tetrahy-
dropyridin-3-yl)-4-phenylbutan-2-one (2j): yield 69%; 0.090 g;
1
colorless oil; [α]23 +93.5 (c 0.4, CHCl3); H NMR (CDCl3, 400
D
MHz) δ 2.36−2.42 (m, 4H), 2.65−2.73 (m, 3H), 2.79−2.88 (m, 4H),
3.02 (dd, 1H, J = 14.5, 11.0 Hz), 3.20−3.25 (m, 1H), 3.89 (dd, 1H, J =
14.5, 6.3 Hz), 4.97 (t, 1H, J = 6.6 Hz), 6.97−7.29 (m, 19H), 7.32−
7.35 (m, 1H), 7.44−7.47 (m, 4H); 13C NMR (CDCl3, 100 MHz) δ
21.6, 29.7, 30.8, 38.1, 42.6, 43.5, 44.6, 58.1, 126.1, 126.4, 127.6, 128.1,
128.2, 128.3, 128.5, 129.0, 129.2, 129.5, 129.6, 133.2, 136.1, 136.4,
136.9, 137.6, 137.7, 139.6, 140.9, 143.2, 198.2, 207.3; IR (NaCl, neat)
I
dx.doi.org/10.1021/jo400121j | J. Org. Chem. XXXX, XXX, XXX−XXX