PAPER
Synthesis of , -Unsaturated Sulfones
1325
2-[1-Octyl-2-(toluene-4-sulfonyl)allyl]malonic Acid Diethyl Ester
(3d)
1H, J = 17.3, 1.5 Hz), 5.75 (m, 1H), 7.03 (t, 1H, J = 7.6 Hz), 7.31 (m,
7H), 7.73 (d, 2H, J = 8.2 Hz).
13C NMR (CDCl3): = 22.3, 26.1, 28.9, 30.0, 44.2, 51.8, 70.4, 73.7,
116.9, 128.3, 128.4, 128.7, 129.1, 130.5, 137.0, 137.6, 139.1, 139.8,
144.9, 145.5.
1H NMR (CDCl3): = 0.89 (m, 3H), 1.27 (m, 16H), 1.55 (m, 3H),
1.68 (m, 1H), 2.43 (s, 3H), 3.14 (m, 1H), 3.81 (d, 1H, J = 5.9 Hz),
4.17 (m, 4H), 5.90 (d, 1H, J = 0.9 Hz), 6.57 (d, 1H, J = 0.9 Hz), 7.37
(d, 2H, J = 8.5 Hz), 7.80 (d, 2H, J = 8.5 Hz).
HRMS (EI): m/z calcd for C24H31NO3S: 413.2025. Found:
413.2002.
(2E)-2-[3,4-Bis-(toluene-4-sulfonyl)but-2-enyl]malonic Acid
Diethyl Ester (3e)
(2E)-[3-Phenyl-2-(toluene-4-sulfonyl)prop-2-enylsulfanyl]-
benzene (3j)
Colorless oil, Rf = 0.3 (hexanes–EtOAc, 5:1).
Yellow oil, Rf = 0.21 (hexanes–EtOAc, 5:1).
IR (neat): = 3058, 2985, 1733, 1444, 1373, 1267, 1150 cm–1.
1H NMR (CDCl3): = 1.26 (t, 6H, J = 7.0 Hz), 2.42 (s, 3H), 2.45 (s,
3H), 2.95 (dd, 2H, J = 7.3, 7.0 Hz), 3.55 (t, 1H, J = 7.0 Hz), 4.18 (q,
4H, J = 7.0 Hz), 4.23 (s, 2H), 7.20 (t, 1H, J = 7.3 Hz), 7.30 (d, 2H,
J = 8.2 Hz), 7.34 (d, 2H, J = 8.2 Hz), 7.66 (d, 2H, J = 8.2 Hz), 7.70
(d, 2H, J = 8.2 Hz).
IR (neat): = 3055, 2986, 2927, 2856, 2300, 1442, 1423, 1266,
1144 cm–1.
1H NMR (CDCl3): = 2.43 (s, 3H), 4.07 (s, 2H), 7.20 (m, 5H), 7.34
(m, 5H), 7.51 (m, 2H), 7.84 (d, 2H, J = 7.2 Hz) 7.95 (s, 1H).
13C NMR (CDCl3): = 28.9, 31.7, 126.9, 127.8, 128.2, 128.3, 128.5,
128.6, 128.9, 129.0, 129.5, 129.8, 130.0, 130.2, 141.1, 144.5.
13C NMR (CDCl3): = 14.7, 22.1, 29.8, 51.0, 54.5, 62.6, 129.1,
129.2, 130.5, 130.6, 135.0, 137.1, 137.9, 145.3, 146.0, 147.7,
168.77.
HRMS (EI): m/z calcd for C22H20O2S2: 380.0905. Found: 380.0902.
HRMS (EI): m/z calcd for C25H30O8S2: 522.1382. Found: 522.1382.
(2E)-Benzyl-[3-phenyl-2-(toluene-4-sulfonyl)allyl]amine (3k)
Colorless solid, mp 120°C (CH2Cl2–hexane); Rf = 0.2 (hexanes–
EtOAc, 5:1).
IR (KBr): = 3055, 3026, 2921, 2849, 1629, 1451, 1290, 1143 cm–1.
(4E)-2,7-Bis-ethoxycarbonyl-4-(toluene-4-sulfonyl)oct-4-enedioic
Acid Diethyl Ester (3f)
Ratio of regioisomers 3f:3g = 4:1.
1H NMR (CDCl3): = 2.42 (s, 3H), 3.41 (s, 2H), 3.73 (s, 2H), 7.30
(m, 10H), 7.59 (d, 2H, J = 7.6 Hz), 7.73 (d, 2H, J = 8.2 Hz), 7.79 (s,
1H).
13C NMR (CDCl3): = 21.6, 44.6, 53.8, 127.1, 128.2, 128.4, 128.5,
128.7, 129.9, 130.1, 133.3, 136.4, 139.2, 139.5, 140.9, 144.3.
Yellow oil, Rf = 0.26 (hexanes–EtOAc, 3:1).
IR (neat): = 3057, 2985, 2936, 2300, 1734, 1373, 1267,1150 cm–1.
1H NMR (CDCl3): = 1.24 (m, 12H), 2.44 (s, 3H), 2.85 (m, 4H),
3.47 (t, 1H, J = 7.3 Hz), 3.99 (t, 1H, J = 7.6 Hz), 4.16 (m, 8H), 6.94
(t, 1H, J = 7.6 Hz), 7.31 (d, 2H, J = 8.2 Hz), 7.70 (d, 2H, J = 8.2 Hz).
HRMS (EI): m/z calcd for C23H23NO2S: 377.1449. Found:
377.1453.
HRMS (EI): m/z calcd for C25H34O10S: 526.1873. Found: 526.1880.
2,5-Bis-ethoxycarbonyl-3-[1-(toluene-4-sulfonyl)vinyl]hexane-
dioic Acid Diethyl Ester (3g)
(2E)-[3-Cyclohexyl-2-(toluene-4-sulfonyl)prop-2-enylsulfanyl]-
benzene (3l)
Colorless oil, Rf = 0.3 (hexanes–EtOAc, 5:1).
IR (neat): = 3055, 2986, 2927, 2856, 2300, 1442, 1423, 1266 cm–1.
1H NMR (CDCl3): = 1.12 (m, 4H), 1.40 (m. 2H), 1.65 (m, 4H),
2.05 (m, 1H), 2.43 (s, 3H), 3.81 (s, 2H), 6.82 (d, 1H, J = 10.6 Hz),
7.16 (m, 2H), 7.22 (m, 3H), 7.30 (d, 2H, J = 8.5 Hz), 7.76 (d, 2H,
J = 8.5 Hz).
13C NMR (CDCl3): = 22.4, 25.9, 26.2, 31.5, 32.4, 39.2, 128.0,
129.1, 129.7, 130.4, 132.2, 136.1, 136.5, 138.2, 144.9, 150.5.
1H NMR (CDCl3): = 1.24 (m, 12H), 2.38 (m, 2H), 2.44 (s, 3H),
3.47 (t, 1H, J = 7.3 Hz), 3.81 (d, 1H, J = 5.9 Hz), 3.99 (m, 1H), 4.16
(m, 8H), 6.00 (d, 1H, J = 1.2 Hz), 6.53 (d, 1H, J = 1.2 Hz), 7.33 (d,
2H, J = 8.2 Hz), 7.76 (d, 2H, J = 8.2 Hz).
(2E)-1-(1-Thiophenylundec-2-ene-2-sulfonyl)-4-methylbenzene
(3h)
Yellow oil, Rf = 0.28 (hexanes–EtOAc, 5:1).
IR (neat): = 3057, 2934, 2929, 2863, 2300, 1625, 1600, 1446,
1308, 1267, 1144 cm–1.
HRMS (EI): m/z calcd for C22H26O2S2: 386.1374. Found: 386.1368.
1H NMR (500 MHz, CDCl3): = 1.46 (m, 2H), 1.53 (m, 2H), 2.01
(m, 2H), 2.43 (s, 3H), 3.41 (t, 2H, J = 5.9 Hz), 3.78 (s, 2H), 4.47 (s,
2H), 6.98 (t, 1H, J = 7.6 Hz), 7.14 (m, 4H), 7.32 (m, 8H), 7.77 (d,
2H, J = 8.2 Hz).
(2E)-Allyl-[3-cyclohexyl-2-(toluene-4-sulfonyl)allyl]amine (3m)
Yellow oil, Rf = 0.22 (hexanes–EtOAc, 3:1).
IR (neat): = 3055, 2983, 2932, 2857, 2300, 1446, 1423, 1267,
1140 cm–1.
1H NMR (CDCl3): = 1.25 (m, 5H), 1.71 (m, 6H), 2.42 (s, 3H), 3.08
(d, 2H, J = 6.2 Hz), 3.36 (s, 2H), 5.06 (dd, 1H, J = 10.6, 1.5 Hz), 5.10
(dd, 1H, J = 17.0, 1.5 Hz), 5.77 (m, 1H), 6.87 (d, 1H, J = 10.3 Hz),
7.30 (d, 2H, J = 7.9 Hz), 7.72 (d, 2H, J = 7.9 Hz).
13C NMR (125 MHz, CDCl3): = 22.4, 25.8, 29.3, 30.0, 31.4, 70.4,
73.7, 128.0, 128.3, 129.1, 129.2, 129.6, 130.4, 132.2, 136.0, 138.0,
138.6, 139.1, 145.0, 146.0.
HRMS (EI): m/z calcd for C27H30NO3S2: 466.1636. Found:
466.1675.
13C NMR (CDCl3): = 21.6, 25.3, 25.6, 32.0, 37.6, 43.6, 50.9,
116.1, 128.0, 136.4, 136.9, 137.1, 144.1, 149.6.
(2E)-Allyl-[7-benzyloxy-2-(toluene-4-sulfonyl)hept-2-enyl]amine
(3i)
Yellow oil, Rf = 0.23 (hexanes–EtOAc, 1:1).
HRMS (EI): m/z calcd for C19H27NO2S: 333.1762. Found:
333.1766.
IR (neat): = 3055, 2981, 2934, 2864, 2300, 1453, 1423, 1266,
1146 cm–1.
1H NMR (CDCl3): = 1.62 (m, 4H), 2.30 (dt, 2H, J = 7.6, 7.3 Hz),
2.42 (s, 3H), 3.06 (d, 2H, J = 5.9 Hz), 3.34 (s, 2H), 3.47 (t, 2H,
J = 5.9 Hz), 4.49 (s, 2H), 5.04 (dd, 1H, J = 10.3, 1.5 Hz), 5.09 (dd,
Acknowledgement
Generous financial support from Korea Research Foundation
(KRF-2000–015-DP0262) is gratefully acknowledged.
Synthesis 2001, No. 9, 1321–1326 ISSN 0039-7881 © Thieme Stuttgart · New York