7532
C. Raji Reddy et al. / Tetrahedron Letters 48 (2007) 7528–7532
1531, 1351, 1026 cmꢀ1
7. Chang, L. L.; Ashton, W. T.; Flanagan, K. L.; Chen,
;
HRMS-ESI: calcd for
T.-B.; O’Malley, S. S.; Zingaro, G. J.; Siegl, P. K. S.;
Kivlighn, S. D.; Lotti, V. J.; Chang, R. S. L.; Greenlee, W.
J. J. Med. Chem. 1994, 37, 4464.
C10H12N2O5NaS, 295.0364; found, 295.0377. N-(Meth-
ylsulfonyl)butyramide (2l): White solid, mp 72–74 °C; H
1
NMR (200 MHz, CDCl3): d 9.23–8.66 (br s, 1H), 3.36 (s,
3H), 2.33 (t, J = 7.3 Hz, 2H), 1.80–1.60 (m, 2H), 0.99 (t,
J = 14.7 Hz, 3H); 13C NMR (75 MHz, CDCl3): d 172.9,
41.5, 38.2, 18.0, 13.5; IR(KBr): m 3198, 2968, 1692, 1460,
1334, 1144, 848 cmꢀ1; HRMS-ESI: calcd for C5H11NO3-
NaS, 188.0357; found, 188.0349. N-Benzyl-N-tosylpropi-
onamide (2n): White solid, mp 159–160 °C; 1H NMR
(200 MHz, CDCl3): d 7.69–7.61 (m, 2H), 7.41–7.22 (m,
7H), 5.11 (s, 2H), 2.56 (q, J = 7.0 Hz, 2H), 2.43 (s, 3H),
1.01 (t, J = 7.8 Hz, 3H); 13C NMR (75 MHz, CDCl3): d
174.1, 144.9, 137.0, 136.9, 129.8, 128.8, 128.0, 127.9, 127.8,
49.6, 29.8, 21.8, 8.8; IR(KBr): m 3396, 2977, 1706, 1354,
8. (a) Wang, Y.; Soper, D. L.; Dirr, M. J.; deLong, M. A.;
De, B.; Wos, J. A. Chem. Pharm. Bull. 2000, 48, 1332; (b)
Musser, J. H.; Kreft, A. F.; Bender, R. H. W.; Kubrak, D.
M.; Grimes, D.; Carlson, R. P.; Hand, J. M.; Chang, J.
J. Med. Chem. 1990, 33, 240.
9. (a) Kondo, K.; Sekimoto, E.; Nakao, J.; Murakami, Y.
Tetrahedron 2000, 56, 5843; (b) Kondo, K.; Sekimoto, E.;
Miki, K.; Murakami, Y. J. Chem. Soc., Perkin Trans. 1
1998, 2973.
10. (a) Ishizuka, N.; Matsumura, K.; Hayashi, K.; Sakai, K.;
Yamamori, T. Synthesis 2000, 6, 784; (b) Ishizuka, N.;
Matsumura, K. Jpn. Kokai Tokkyo Koho JP 10045705;
Chem. Abstr. 1998, 128, 140463; (c) Inoe, T.; Myahara, O.;
Takahashi, A.; Nakamura, Y. Jpn. Kokai Tokkyo Koho
JP 08198840; Chem. Abstr. 1996, 125, 247385.
11. (a) Yijima, C.; Hino, F.; Suda, K. Synthesis 1981, 610; (b)
Shanguann, N.; Katukojvala, S.; Greenberg, R.; Williams,
L. J. J. Am. Chem. Soc. 2003, 125, 7754.
12. EDCÆHCl: (a) Berry, D. J.; Digiovanna, C. V.; Metrick, S.
S.; Murugan, R. ARKIVOC 2001, i, 201; (b) Guzzo, P. R.;
Teng, M.; Miller, M. J. Tetrahedron 1994, 50, 8275; CDI:
(c) Drummond, J. T.; Johnson, G. Tetrahedron Lett. 1988,
29, 1653; DCC: (d) Johnson, D. C., II.; Widlanski, T. S.
Tetrahedron Lett. 2001, 42, 3677; (e) Gomes, P.; Gomes, J.
R. B.; Rodrigues, M.; Moreira, R. Tetrahedron 2003, 59,
7473; (f) Wang, Y.; Sarris, K.; Sauer, D. R.; Djuric, S. W.
Tetrahedron Lett. 2007, 48, 5181.
1158, 1011, 729, 585 cmꢀ1
; HRMS-ESI: calcd for
C17H19NO3NaS, 340.0983; found: 340.0991. N-Benzyl-N-
(methylsulfonyl)acetamide (2o): White solid, mp 73–75 °C;
1H NMR (200 MHz, CDCl3): d 7.43–7.29 (m, 5H), 5.02
(m, 2H), 3.13 (s, 3H), 2.35 (s, 3H); 13C NMR (75 MHz,
CDCl3): d 171.3, 136.2, 128.9, 128.0, 127.4, 49.3, 42.7,
24.8; IR (KBr): m 3386, 2933, 1707, 1450, 1338, 1161, 960,
832, 511 cmꢀ1; HRMS-ESI: calcd for C10H13NO3NaS,
250.0513; found, 250.0520. N-Benzyl-N-(methylsulfon-
yl)propionamide (2p): Viscous liquid; 1H NMR
(200 MHz, CDCl3): d 7.43–7.29 (m, 5H), 5.02 (m, 2H),
3.20 (s, 3H), 2.59 (q, J = 7.3 Hz, 2H), 1.15 (t, J = 7.3 Hz,
3H); 13C NMR (75 MHz, CDCl3): d 174.9, 136.4, 129.0,
127.9, 127.1, 48.9, 42.7, 29.6, 8.7; IR(Neat): m 2984, 2940,
1701, 1454, 1351, 1159, 956, 779, 515 cmꢀ1; HRMS-ESI:
calcd for C11H15NO3NaS, 264.0670; found, 264.0661.
(R)-N-(Methylsulfonyl)-N-(1-phenylethyl)acetamide (2q):
13. Katritzky, A. R.; Hoffmann, S.; Sukuki, K. ARKIVOC
2004, xii, 14.
25
Viscous liquid; ½aꢁD ꢀ59.4 (c 1 in CHCl3); 1H NMR
14. (a) Greene, T. W.; Wuts, P. G. M. Protecting Groups in
Organic Synthesis, 3rd ed.; John Wiley & Sons: New York,
1999; (b) Ishihara, K.; Kubota, M.; Kurihara, H.;
Yamamoto, H. J. Org. Chem. 1996, 1, 4560; (c) Orita,
A.; Tanahashi, C.; Kakuda, A.; Otera, J. J. Org. Chem.
2001, 66, 8926; (d) Chen, C.-T.; Kuo, J.-H.; Pawar, V. D.;
Munot, Y. S.; Weng, S.-S.; Ku, C.-H.; Liu, C.-Y. J. Org.
Chem. 2005, 70, 1188; (e) Chakraborti, A. K.; Shivani J.
Org. Chem. 2006, 71, 5785, and references cited therein.
15. (a) Mosisowa, Y.; Kataoka, M.; Negahori, H.; Sakamoto,
T.; Kitano, N.; Kusano, K. J. Med. Chem. 1980, 23, 1376;
(b) Martin, M. T.; Roschangar, F.; Eaddy, J. F. Tetra-
hedron Lett. 2003, 44, 5461; (c) Singh, D. U.; Singh, P. R.;
Samant, S. D. Tetrahedron Lett. 2004, 45, 4805.
16. In order to check the efficiency of the method, a large scale
(3 g) acylation of benzene sulfonamide was also carried
out using 3 mol % of ZnCl2 and the reaction proceeded in
8 minutes to give the product 2a in 96% yield.
17. The enantiomers of compound 4g show activity in
reperfusion injury treatment and one of the enantiomers
(R-enantiomer, repertaxin) was selected as a clinical
candidate that is now in phase II clinical studies for the
prevention of reperfusion injury; see Ref. 2b.
(200 MHz, CDCl3): d 7.59–7.18 (m, 5H), 5.85 (q,
J = 7.0 Hz, 1H), 3.10 (s, 3H), 2.23 (s, 3H), 1.86 (d,
J = 7.0 Hz, 3H); 13C NMR (75 MHz, CDCl3): d 171.4,
139.5, 128.6, 127.7, 127.1, 55.6, 43.2, 25.9, 18.4; IR (KBr):
m 3028, 2938, 1694, 1349, 1238, 1163, 949, 770, 550 cmꢀ1
;
HRMS-ESI: (M+H)+ calcd for C11H15NO3NaS,
264.0670; found: 264.0672. N-(Phenylsulfonyl)hex-5-yna-
mide (4a): White solid, mp 73–75 °C; 1H NMR (200 MHz,
CDCl3): d 9.12–8.80 (br s, 1H), 8.17–8.02 (m, 2H), 7.75–
7.49 (m, 3H), 2.44 (t, J = 6.8 Hz, 2H), 2.25–2.10 (m, 2H),
1.96–1.69 (m, 3H); 13C NMR (75 MHz, CDCl3): d 170.8,
139.6, 134.3, 129.2, 128.4, 83.0, 69.8, 34.8, 22.8, 17.6;
IR(neat): m 3272, 3129, 1683, 1458, 1166, 686 cmꢀ1
;
HRMS-ESI: (M+H)+ calcd for C12H14NO3S, 252.0694;
found, 252.0704. N-(Phenylsulfonyl)cinnamamide (4b):
White solid, mp 152–154 °C; 1H NMR (200 MHz,
CDCl3): d 9.40–9.10 (br s, 1H), 8.22–8.08 (m, 1H), 7.80–
7.27 (m, 10H), 6.48 (d, J = 15.6 Hz, 1H); 13C NMR
(75 MHz, CDCl3): d 163.8, 146.4, 138.7, 134.2, 133.8,
131.1, 129.2, 129.1, 128.6, 128.5, 117.5; IR(KBr): m 3289,
1697, 1626, 1426, 1085 cmꢀ1; HRMS-ESI: calcd for
C15H13NO3NaS, 310.0513; found, 310.0515. 2-(3,4-
Dimethoxyphenyl)-N-(phenylsulfonyl)acetamide
(4d):
18. Spectral data for new products: N-(4-Nitrophenylsulfon-
yl)acetamide (2i): Pale yellow solid, mp 197–199 °C; 1H
NMR (200 MHz, CDCl3): d 8.40–8.32 (m, 2H), 8.28–8.20
(m, 2H), 3.23–2.31 (br s, 1H), 2.04 (s, 3H); 13C NMR
(75 MHz, CDCl3): d 169.2, 150.2, 144.5, 129.2, 124.4, 23.2;
IR(KBr): m 3109, 2922, 1717, 1693, 1533, 1465, 1351,
Semi solid, 1H NMR (200 MHz, CDCl3): d 8.06–7.94
(m, 1H), 7.74–7.43 (m, 3H), 6.88–6.57 (m, 4H), 3.87 (s,
3H), 3.79 (s, 3H), 3.53 (s, 2H); 13C NMR (75 MHz,
CDCl3):d 169.0, 149.6, 149.0, 138.5, 134.2, 128.8, 128.5,
124.7, 121.8, 112.3, 112.0, 56.0, 43.5; IR(KBr): m 3425,
2924, 1696, 1454, 1166 cmꢀ1; EIMS: m/z 358.1 (M+Na).
N-(Phenyl sulfonyl)-4-oxopentanamide (4e): Semi solid, 1H
NMR (300 MHz, DMSO-d6): d 7.71–7.60 (m, 2H), 7.51–
7.32 (m, 3H), 2.48 (t, J = 6.2 Hz, 2H), 2.20 (t, J = 6.2 Hz,
2H), 1.92 (s, 3H); 13C NMR (75 MHz, DMSO-d6): d
207.2, 173.9, 144.2, 132.0, 129.0, 125.6, 37.6, 29.7, 27.7;
609 cmꢀ1
;
HRMS-ESI: calcd for C8H8N2O5NaS,
267.0051; found, 267.0055. N-(4-Nitrophenylsulfonyl)-
1
butyramide (2j): Semi solid, H NMR (200 MHz, CDCl3):
d
8.40–8.32 (m, 2H), 8.28–8.20 (m, 2H), 2.23 (t,
J = 7.3 Hz, 2H), 1.66–1.46 (m, 2H), 0.86 (t, J = 7.3 Hz,
3H); 13C NMR (75 MHz, CDCl3): d 171.8, 150.2, 144.7,
129.2, 124.4, 37.2, 17.4, 13.1; IR(neat): m 3426, 1715, 1651,
IR(KBr): m 3349, 3256, 1714, 1695, 1448, 1334 cmꢀ1
EIMS: m/z 278.0 (M+Na).
;