The Journal of Organic Chemistry
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(d, J = 8.8 Hz, 1H), 7.38−7.31 (m, 2H), 7.29−7.23 (m, 1H), 7.19−
7.14 (m, 1H), 6.26 (ddd, J = 17.1, 10.3, 6.5 Hz, 1H), 5.38 (dt, J = 10.3,
1.1 Hz, 1H), 5.15 (d, J = 6.5 Hz, 1H), 4.98 (dt, J = 17.1, 1.1 Hz, 1H),
2.87 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 151.5, 146.0, 140.5,
137.7, 137.4, 128.9, 128.5, 127.3, 125.8, 123.6, 122.1, 118.7, 48.4, 38.4;
IR (KBr) ν (cm−1) 3028, 2952, 1527, 1348, 1263, 1124; HRMS (ESI)
calcd. for C16H15NO5S [M + H]+ m/z 334.0744, found 334.0750.
4-Nitro-2-(1-phenylbut-2-en-1-yl)phenyl methanesulfonate (3b).
Yellowish oil, E/Z = 4:1, 42 mg, 12% yield (170 mg, 49% in DMF): 1H
NMR (400 MHz, CDCl3) δ 8.26 and 8.21 (d, J = 2.8 Hz, 1H), 8.15
(dd, J = 8.9, 2.8 Hz, 1H), 7.60 (d, J = 8.9 Hz, 1H), 7.34−7.29 (m, 2H),
7.25−7.21 (m, 1H), 7.18−7.14 (m, 2H), 5.87 (ddq, J = 15.2, 7.1, 1.6
Hz) and 5.80 (dd, J = 10.5, 8.1 Hz) (1H), 5.79 (dq, J = 10.5, 5.0 Hz)
and 5.45 (ddq, J = 15.2, 6.6, 1.2 Hz) (1H), 5.40 (d, J = 8.1 Hz) and
5.08 (d, J = 7.1 Hz) (1H), 2.87 and 2.84 (s, 3H), 1.77 (dt, J = 6.6, 1.2
Hz) and 1.73 (d, J = 5.0 Hz) (3H); 13C NMR (100 MHz, CDCl3) δ
151.5, 151.4, 146.0, 145.9, 141.5, 138.6, 138.3, 130.6, 130.1, 129.6,
128.9, 128.8, 128.3, 127.8, 127.4, 127.0, 126.9, 125.7, 125.4, 123.4,
122.1, 122.0, 47.6, 42.6, 38.3, 18.0, 13.3; IR (KBr) ν (cm−1) 3028,
1585, 1349, 1217, 1074, 971. HRMS (ESI) calcd. for C17H17NO5S [M
+ Na]+ m/z 370.0719, found 370.0725.
5.74−5.66 (m, 1H), 5.80−5.76 (m) and 5.40 (dqd, J = 15.2, 6.4, 1.3
Hz) (1H), 5.38 (d, J = 7.9 Hz) and 5.04 (d, J = 7.2 Hz) (1H), 2.84 and
2.79 (s, 3H), 2.32 and 2.31 (s, 3H), 1.73 (dt, J = 6.5, 1.3 Hz) and 1.70
(d, J = 6.6 Hz) (3H); 13C NMR (100 MHz, CDCl3) δ 145.3, 143.7,
143.0, 137.0, 136.8, 136.5, 136.0, 132.1, 131.6, 130.8, 130.6, 128.5,
128.4, 128.3, 128.03, 127.9, 126.4, 126.3, 125.9, 121.2, 121.1, 47.2,
42.0, 37.6, 37.5, 21.0, 18.0, 13.2; IR (KBr) ν (cm−1) 3027, 2938, 2856,
1600, 1492, 1451, 1198, 970, 700; HRMS (ESI) calcd. for C18H20O3S
[M + Na]+ m/z 339.1025, found 339.1021.
4-Methoxy-2-(1-phenylbut-2-en-1-yl)phenyl methanesulfonate
(3g). Yellowish oil, E/Z = 6:1, 33 mg, 10% yield (136 mg, 41% in
DMF): 1H NMR (400 MHz, CDCl3) δ 7.34−7.26 (m, 3H), 7.22−7.17
(m, 3H), 6.85−6.73 (m, 2H), 5.84 (ddq, J = 15.2, 7.1, 1.5 Hz) and
5.73−5.67 (m, 1H), 5.81−5.74 (m) and 5.40 (dqd, J = 15.2, 6.5, 1.3
Hz) (1H), 5.38 (d, J = 7.9 Hz) and 5.04 (d, J = 7.0 Hz) (1H), 3.77 and
3.76 (s, 3H), 2.86 and 2.81 (s, 3H), 1.73 (dt, J = 6.5, 1.3 Hz, 3H); 13C
NMR (100 MHz, CDCl3) δ 158.0, 142.7, 140.9, 137.9, 131.9, 131.4,
128.5, 128.4, 128.1, 128.0, 126.5, 126.4, 126.2, 122.5, 122.5, 116.3,
115.8, 112.0, 111.8, 55.5, 47.4, 42.3, 37.5, 37.5, 18.0, 13.2; IR (KBr) ν
(cm−1) 3027, 2939, 2855, 1600, 1585, 1489, 1452, 1196, 1063, 970,
701; HRMS (ESI) calcd. for C18H20O4S [M + Na]+ m/z 355.0975,
found 355.0964.
4-Nitro-2-(1-phenylprop-1-en-1-yl)phenyl methanesulfonate
(4a). Yellowish oil, E/Z = 5:1, 13 mg, 4% yield (77 mg, 23% in
DMF): 1H NMR (400 MHz, CDCl3) δ 8.28 and 8.18 (dd, J = 9.0, 2.8
Hz, 1H), 8.25 and 8.18 (d, J = 2.8 Hz, 1H), 7.64 and 7.56 (d, J = 9.0
Hz, 1H), 7.39−7.24 (m, 3H), 7.22−7.17 (m, 2H), 6.44 and 6.10 (q, J
= 7.1 Hz, 1H), 2.77 and 2.71 (s, 3H), 1.95 and 1.74 (d, J = 7.1 Hz,
3H); 13C NMR (100 MHz, CDCl3) δ 151.5, 145.9, 140.3, 138.2,
138.2, 136.6, 135.8, 134.0, 131.1, 129.3, 128.7, 128.4, 127.8, 127.7,
127.6, 127.1, 126.3, 124.3, 123.8, 123.3, 122.5, 38.7, 38.2, 15.9, 15.7; IR
(KBr) ν (cm−1) 3028, 1528, 1350, 1251, 1124, 970, 865, 733; HRMS
(ESI) calcd. for C16H15NO5S [M + H]+ m/z 334.0744, found
334.0748.
4-Nitro-2-(1-phenylbut-1-en-1-yl)phenyl methanesulfonate (4b).
Yellowish oil, 10 mg, 3% yield (45 mg, 13% in DMF): 1H NMR (400
MHz, CDCl3) δ 8.27 (dd, J = 9.0, 2.8 Hz, 1H), 8.18 (d, J = 2.8 Hz,
1H), 7.63 (d, J = 9.0 Hz, 1H), 7.32−7.29 (m, 3H), 7.21−7.19 (m,
2H), 2.75 (s, 3H), 2.05 (p, J = 7.5 Hz, 2H), 1.07 (t, J = 7.5 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ 151.5, 145.8, 140.2, 135.6, 134.2,
4-Cyano-2-(1-phenylallyl)phenyl methanesulfonate (3c). Color-
1
less oil, 185 mg, 59% yield (31 mg, 10% in DMF): H NMR (400
MHz, CDCl3) δ 7.60 (dd, J = 8.3, 2.0 Hz, 1H), 7.58 (d, J = 2.0 Hz,
1H), 7.56 (d, J = 8.3 Hz, 1H), 7.37−7.31 (m, 2H), 7.29−7.24 (m,
1H), 7.15 (d, J = 7.2 Hz, 2H), 6.21 (ddd, J = 17.2, 10.3, 6.4 Hz, 1H),
5.35 (dt, J = 10.3, 1.2 Hz, 1H), 5.13 (d, J = 6.4 Hz, 1H), 4.93 (d, J =
17.2 Hz, 1H), 2.89 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 150.2,
140.5, 137.8, 137.3, 134.5, 132.1, 128.8, 128.5, 127.2, 122.4, 118.5,
117.9, 111.0, 48.0, 38.4; IR (KBr) ν (cm−1) 3028, 2936, 2232, 1372,
1169, 1095, 970. HRMS (ESI) calcd. for C17H15NO3S [M + Na]+ m/z
336.0664, found 336.0670.
4-Cyano-2-(1-phenylbut-2-en-1-yl)phenyl methanesulfonate
(3d). Colorless oil, E/Z = 4:1, 78 mg, 24% yield (176 mg, 54% in
DMF): 1H NMR (400 MHz, CDCl3) δ 7.65−7.53 (m, 3H), 7.33−7.29
(m, 2H), 7.25−7.22 (m, 1H), 7.16−7.12 (m, 2H), 5.81 (ddq, J = 15.3,
7.0, 1.6 Hz) and 5.74 (dd, J = 10.6, 7.8 Hz) (1H), 5.73 (ddq, J = 10.6,
5.2, 1.6 Hz) and 5.40 (ddq, J = 15.3, 6.5, 1.3 Hz) (1H), 5.37 (d, J = 7.8
Hz) and 5.05 (d, J = 7.1 Hz) (1H), 2.87 and 2.84 (s, 3H), 1.76 (dt, J =
6.5, 1.2 Hz) and 1.71 (d, J = 5.2 Hz,) (3H); 13C NMR (100 MHz,
CDCl3) δ 150.3, 150.2, 142.4, 141.5, 138.6, 138.2, 134.4, 134.1, 131.8,
130.7, 130.2, 129.4, 128.8, 128.7, 128.4, 127.9, 127.3, 127.0, 126.9,
122.4, 122.3, 118.0, 117.9, 111.0, 110.8, 47.3, 42.3, 38.3, 18.0, 13.2; IR
(KBr) ν (cm−1) 3027, 2232, 1358, 1168, 972, 701; HRMS (ESI) calcd.
for C18H17NO3S [M + Na]+ m/z 350.0821, found 350.0822.
130.6, 128.7, 127.7, 126.4, 124.3, 123.2, 122.0, 38.7, 23.6, 13.8; IR
(KBr) ν (cm−1) 3025, 1578, 1349, 1209, 1077, 970, 857; HRMS (ESI)
calcd. for C17H17NO5S [M + H]+ m/z 348.0900, found 348.0907.
4-Cyano-2-(1-phenylprop-1-en-1-yl)phenyl methanesulfonate
(4c). Colorless oil, E/Z = 6:1, 6 mg, 2% yield (25 mg, 8% in
DMF): 1H NMR (400 MHz, CDCl3) δ 7.71 and 7.63 (dd, J = 8.6, 2.1
Hz, 1H), 7.65 and 7.60 (d, J = 2.1 Hz, 1H), 7.59 and 7.50 (d, J = 8.6
Hz, 1H), 7.39−7.24 (m, 3H), 7.20−7.16 (m, 2H), 6.41 and 6.05 (q, J
= 7.1 Hz, 1H), 2.76 and 2.71 (s, 3H), 1.93 and 1.72 (d, J = 7.1 Hz,
3H); 13C NMR (101 MHz, CDCl3) δ 150.3, 140.4, 136.4, 135.7,
135.7, 134.1, 132.9, 132.3, 130.8, 129.3, 128.6, 128.4, 128.2, 127.6,
127.6, 126.3, 123.7, 122.9, 117.7, 111.1, 38.7, 38.2, 15.9, 15.7; IR
(KBr) ν (cm−1) 3112, 2232, 1372, 1169, 1085, 970, 858, 701. HRMS
(ESI) calcd. for C17H15NO3S [M + H]+ m/z 314.0845, found
314.0849.
(S)-4-Cyano-2-(1-phenylbut-2-en-1-yl)phenyl methanesulfonate
20
((S)-3d). Colorless oil, E/Z = 19:1, 81 mg, 25% yield: [α]D
=
1
+25.0 (c 1.0, CHCl3); H NMR (400 MHz, CDCl3) δ 7.61−7.54 (m,
3H), 7.34−7.30 (m, 2H), 7.26−7.23 (m, 1H), 7.14−7.12 (m, 2H),
5.81 (dd, J = 15.2, 6.9 Hz, 1H), 5.40 (dq, J = 15.2, 6.4 Hz, 1H), 5.05
(d, J = 6.8 Hz, 1H), 2.87 and 2.84 (s, 3H), 1.76 (d, J = 6.2 Hz) and
1.71 (d, J = 6.5 Hz,) (3H).
4-Cyano-2-(1-(p-tolyl)but-2-en-1-yl)phenyl methanesulfonate
(3e). Colorless oil, E/Z = 4:1, 17 mg, 5% yield (211 mg, 62% in
1
DMF): H NMR (400 MHz, CDCl3) δ 7.63 and 7.59 (d, J = 2.0 Hz,
1H), 7.57 (dd, J = 8.5, 2.0 Hz, 1H), 7.53 (d, J = 8.5 Hz, 1H), 7.12 (d, J
= 7.9 Hz, 2H), 7.04−7.0 (m, 2H), 5.80 (ddq, J = 15.3, 6.9, 1.4 Hz) and
5.71 (dd, J = 10.5, 7.5 Hz) (1H), 5.72 (ddq, J = 10.5, 5.3, 1.3 Hz) and
5.38 (ddq, J = 15.3, 6.5, 1.2 Hz) (1H), 5.34 (d, J = 6.9 Hz) and 5.01
(d, J = 6.9 Hz) (1H), 2.90 and 2.87 (s, 3H), 2.32 (s, 3H), 1.75 (dt, J =
6.5, 1.2 Hz) and 1.70 (d, J = 5.3 Hz) (3H); 13C NMR (100 MHz,
CDCl3) δ 150.2, 150.2, 139.3, 138.9, 138.4, 136.7, 136.6, 134.4, 134.1,
131.7, 130.9, 130.4, 129.5, 129.4, 129.1, 128.3, 127.7, 127.0, 122.4,
122.3, 118.0, 118.0, 111.0, 110.8, 46.8, 41.9, 38.3, 21.0, 18.0, 13.2; IR
(KBr) ν (cm−1) 3117, 2231, 1370, 1223, 1167, 971, 730; HRMS (ESI)
calcd. for C19H19NO3S [M + H]+ m/z 342.1158, found 342.1159.
4-Methyl-2-(1-phenylbut-2-en-1-yl)phenyl methanesulfonate
(3f). Yellowish oil, E/Z = 6:1, 47 mg, 15% yield (117 mg, 37% in
DMF): 1H NMR (400 MHz, CDCl3) δ 7.23−7.26 (m, 3H), 7.22−7.16
(m, 3H), 7.12−7.02 (m, 2H), 5.86 (ddq, J = 15.2, 7.2, 1.5 Hz) and
4-Cyano-2-(1-phenylbut-1-en-1-yl)phenyl methanesulfonate
(4d). Colorless oil, 13 mg, 4% yield (88 mg, 27% in DMF): 1H
NMR (400 MHz, CDCl3) δ 7.71−7.69 (m, 1H), 7.59−7.57 (m, 2H),
7.32−7.26 (m, 3H), 7.19−7.17 (m, 2H), 6.29 (t, J = 7.5 Hz, 1H), 2.74
(s, 3H), 2.03 (p, J = 7.5 Hz, 2H), 1.06 (t, J = 7.5 Hz, 3H);13C NMR
(100 MHz, CDCl3) δ 150.2, 140.3, 136.2, 135.5, 134.3, 134.0, 132.8,
128.6, 127.7, 126.3, 123.6, 117.7, 110.9, 38.7, 23.5, 13.9; IR (KBr) ν
(cm−1) 3024, 2232, 1363, 1169, 1093, 970, 832; HRMS (ESI) calcd.
for C18H17NO3S [M + Na]+ m/z 350.0821, found 350.0822.
4-Cyano-2-(1-(p-tolyl)but-1-en-1-yl)phenyl methanesulfonate
1
(4e). Colorless oil, 10 mg, 3% yield (14 mg, 4% in DMF): H NMR
(400 MHz, CDCl3) δ 7.69 (dd, J = 8.6, 2.1 Hz, 1H), 7.57 (d, J = 2.1
Hz, 2H), 7.57 (d, J = 8.6 Hz, 1H), 7.10 (d, J = 8.2 Hz, 2H), 7.06 (d, J
= 8.2 Hz, 2H), 6.25 (t, J = 7.5 Hz, 1H), 2.76 (s, 3H), 2.32 (s, 3H), 2.00
(p, J = 7.5 Hz, 2H), 1.05 (t, J = 7.5 Hz, 3H); 13C NMR (100 MHz,
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dx.doi.org/10.1021/jo302210t | J. Org. Chem. 2012, 77, 10856−10869