X.-W. Wang et al. / Tetrahedron 67 (2011) 7618e7621
7621
7.73e7.46 (m, 6H), 7.09e6.76 (m, 5H), 6.54e6.49 (m, 3H), 6.15 (s,
1H); 13C NMR (100 MHz, CDCl3): 162.4, 162.0, 138.2 (m, J¼31 Hz),
134.2, 133.3, 131.6 (m, J¼6.5 Hz), 130.8, 130.4, 129.8, 128.8, 128.5,
128.4, 128.2, 127.4, 126.8, 126.3, 125.0, 124.7, 124.1, 122.0 (m,
185e186 ꢁC; IR (CH2Cl2, film): 3411, 2925, 2225, 1676, 1588, 1445,
1174, 1072, 964 cmꢀ1 1H NMR (300 MHz, CDCl3):
;
d¼7.87 (s, 1H),
7.29e7.25 (m, 1H), 7.20e7.15 (m, 3H), 7.05e7.03 (m, 3H), 6.72 (d,
J¼8.4 Hz, 2H), 6.44 (s, 1H), 6.11 (s, 1H); 13C NMR (100 MHz, CDCl3):
163.1,162.1,136.9,135.9 (m, J¼30 Hz),134.6 (m, J¼6.0 Hz),133.1,130.9,
130.7, 130.5, 128.9, 128.3, 124.7 (m, J¼270 Hz), 123.6, 117.0, 108.1; 19F
J¼274 Hz), 116.7, 111.4; 19F NMR (CDCl3):
¼ꢀ66.6 (s, 3F); MS (ESI)
d
(m/z): 415 (MþNaþ); HRMS calcd for, C23H15F3N2ONa: 415.1034
found: 415.1028.
NMR (CDCl3):
d
¼ꢀ65.7 (s, 3F); MS (ESI) (m/z): 443 (MþNaþ); HRMS
calcd for C19H12BrF3N2ONa: 442.9983, found: 442.9977.
4.2.7. (2E,4E)-2-Cyano-6,6,6-trifluoro-5-phenyl-3-p-tolylhexa-2,4-
dienamide (3g). Yield: 89%; yellow solid; mp: 164e165 ꢁC; IR (CH2Cl2,
4.2.13. (2E,4E)-2-Cyano-6,6,6-trifluoro-3-phenyl-5-p-tolylhexa-2,4-
dienamide (3m). Yield: 89%; yellow solid; mp: 168e169 ꢁC; IR
(CH2Cl2, film): 3440, 3159, 2200, 1694, 1611, 1446, 1180, 1081,
film): 3334, 2923, 2226, 1724, 1689, 1445, 1173, 1076, 962 cmꢀ1 1H
;
NMR (300 MHz, CDCl3):
d
¼7.80 (s, 1H), 7.17e7.03 (m, 4H), 6.99e6.87
(m, 6H), 6.40 (s, 1H), 6.19 (s, 1H), 2.25 (s, 3H); 13C NMR (100 MHz,
CDCl3): 163.7, 162.5, 141.1, 136.7 (m, J¼31 Hz),134.1 (m, J¼5.7 Hz),131.7,
129.7,129.4,128.9,128.8,128.8,127.7,122.9 (m, J¼267 Hz),117.5,106.9,
961 cmꢀ1; 1H NMR (300 MHz, CDCl3):
d
¼8.07 (s, 1H), 7.48e7.29 (m,
5H), 7.12e7.00 (m, 4H), 6.68 (s, 1H), 6.51 (s, 1H), 2.47 (s, 3H); 13C
NMR (100 MHz, CDCl3): 163.8, 162.4, 139.1, 137.2 (m, J¼30 Hz), 137.1,
133.5 (m, J¼5.9 Hz), 130.3, 129.3, 128.9, 128.7, 128.6, 128.0, 123.8 (m,
21.3; 19F NMR (CDCl3):
d
¼ꢀ65.6 (s, 3F); MS (ESI) (m/z): 379 (MþNaþ);
HRMS calcd for C20H15F3N2ONa: 379.1034, found: 379.1029.
J¼273 Hz), 117.3, 107.8, 21.1; 19F NMR (CDCl3):
¼ꢀ65.6 (s, 3F); MS
d
(ESI) (m/z): 379 (MþNaþ); HRMS calcd for C20H15F3N2ONa:
4.2.8. (2E,4E)-2-Cyano-6,6,6-trifluoro-3-(4-(trifluoromethyl)phe-
nyl)-5-phenylhexa-2,4-dienamide (3h). Yield: 86%; yellow solid;
mp: 145e146 ꢁC; IR (CH2Cl2, film): 3413, 3196, 2230, 1732, 1596,
379.1034, found: 379.1029.
4.2.14. (2E,4E)-2-Cyano-6,6,6-trifluoro-5-methyl-3-phenylhexa-2,4-
dienamide (3n). Yield: 65%; white solid; mp: 132e133 ꢁC; IR
(CH2Cl2, film): 3437, 3168, 2205, 1698, 1612, 1446, 1189, 1097,
1446, 1172, 1064, 965 cmꢀ1
;
1H NMR (300 MHz, CDCl3):
d¼7.92 (s,
1H), 7.35e7.32 (m, 3H), 7.13e7.01 (m, 5H), 6.83e6.80 (m, 3H), 6.49
(s, 1H), 6.35 (s, 1H); 13C NMR (100 MHz, CDCl3): 161.8, 161.7, 140.4,
138.4 (m, J¼31 Hz), 133.1 (m, J¼6.7 Hz), 131.7 (m, J¼33 Hz), 131.5,
129.5, 129.3, 129.1, 128.2, 125.0 (m, J¼3.7 Hz), 123.3 (m, J¼270 Hz),
896 cmꢀ1; 1H NMR (300 MHz, CDCl3):
d
¼7.51e7.48 (m, 6H), 6.41 (s,
1H), 6.26 (s, 1H), 1.36 (s, 3H); 13C NMR (100 MHz, CDCl3): 162.2,
161.9, 136.9, 133.7 (m, J¼30 Hz), 131.4, 129.4 (m, J¼6.6 Hz), 129.2,
128.8, 123.9 (m, J¼272 Hz), 117.4, 107.8, 13.0; 19F NMR (CDCl3):
122.7 (m, J¼273 Hz), 116.5, 109.5; 19F NMR (CDCl3):
¼ꢀ66.5 (s, 3F),
d
ꢀ63.7 (s, 3F); MS (ESI) (m/z): 433 (MþNaþ); HRMS calcd for
d
¼ꢀ70.3 (s, 3F); MS (ESI) (m/z): 303 (MþNaþ); HRMS calcd for
C20H12F6N2ONa: 433.0752, found: 433.0746.
C14H11F3N2ONa: 303.0721, found: 303.0716.
4.2.9. (2Z,4E)-2-Cyano-6,6,6-trifluoro-4-methyl-3,5-diphenylhexa-
2,4-dienamide (3i). Yield: 86%; yellow solid; mp: 165e166 ꢁC; IR
(CH2Cl2, film): 3453, 3154, 2211, 1697, 1582, 1444, 1186, 1027,
Acknowledgements
This research was supported by the National Natural Science
Foundation of China (No.21032006, 20172064), the QT Program,
Shanghai Natural Science Council.
919 cmꢀ1
;
1H NMR (300 MHz, CDCl3):
d
¼7.40e7.33 (m, 1H),
7.27e7.18 (m, 3H), 7.13e7.08 (m, 4H), 6.88 (d, J¼6.9 Hz, 2H), 6.29 (s,
1H), 6.20 (s, 1H), 2.38 (s, 3H); 13C NMR (100 MHz, CDCl3): 169.8,
161.9, 145.7 (m, J¼6.9 Hz), 136.5, 134.0, 131.2, 129.3, 129.0 (m,
J¼27 Hz), 128.5, 128.2, 127.9, 123.4 (m, J¼273 Hz), 117.6, 105.4, 21.0;
Supplementary data
19F NMR (CDCl3):
d
¼ꢀ68.4 (s, 3F); MS (ESI) (m/z): 379 (MþNaþ);
Supplementary data associated with this article can be found, in
clude MOL files and InChIKeys of the most important compounds
described in this article.
HRMS calcd for C20H15F3N2ONa: 379.1034, found: 379.1029.
4.2.10. (2E,4E)-2-Cyano-6,6,6-trifluoro-5-(naphthalen-3-yl)-3-
phenylhexa-2,4-dienamide (3j). Yield: 83%; yellow solid; mp:
199e200 ꢁC;IR (CH2Cl2, film): 3453, 3146, 2212,1694,1591,1463,1175,
References and notes
1077, 946 cmꢀ1
;
1H NMR (300 MHz, CDCl3):
d
¼8.22 (s, 1H), 7.73 (t,
J¼7.8 Hz, 2H), 7.60 (d, J¼8.4 Hz,1H), 7.45e7.40 (m, 2H), 7.04e6.98 (m,
2H), 6.88e6.80 (m, 3H), 6.53 (d, J¼8.1 Hz, 2H), 6.42 (s,1H), 6.24 (s,1H);
13C NMR (100 MHz, CDCl3): 163.9, 162.2, 136.6, 135.9 (m, J¼5.9 Hz),
135.2 (m, J¼31 Hz), 133.1, 132.0, 129.9, 129.3, 128.5, 128.1, 128.0, 127.9,
127.8, 127.7, 126.6, 126.0, 125.1, 124.5, 123.0 (m, J¼273 Hz),116.9,107.6;
1. (a) Filler, R.; Kobayashi, Y. Biomedicinal Aspects of Fluorine Chemistry; Kodansha
& Elsevier Biomedical: Tokyo, 1982; (b) Filler, R.; Banks, R. E. Organofluorine
Chemicals and their Industrial Applications; Horwood: London, 1979; (c) Welch,
J. T. Tetrahedron 1987, 43, 3123; (d) Filler, R.; Kobayashi, Y.; Yagupolskii, L. M.
Organofluorine Compounds in Medicinal Chemistry and Biomedical Applications;
Elsevier: Amsterdam, 1993.
2. McAlonan, H.; Murphy, J. P.; Nieuwenhuyzen, M.; Reynolds, K.; Sarma, P. K. S.;
Stevenson, P. J.; Thompson, N. J. Chem. Soc., Perkin Trans. 1 2002, 69.
3. (a) Huang, Y.; Iwama, T.; Rawal, V. H. J. Am. Chem. Soc. 2000, 122, 7843; (b) Evans,
D. A.; Miller, S. J.; Lectka, T.; von Matt, P. J. Am. Chem. Soc. 1999, 121, 7559; (c)
Overman, L. E.; Lesuisse, D.; Hashimoto, M. J. Am. Chem. Soc. 1983, 105, 5373; (d)
Overman, L. E.; Freerks, R. L. J. Org. Chem. 1981, 46, 2833.
19FNMR (CDCl3):
d
¼ꢀ65.8 (s, 3F); MS (ESI) (m/z): 415 (MþNaþ); HRMS
calcd for, C23H15F3N2ONa: 415.1034, found: 415.1028.
4.2.11. (2E,4E)-5-(4-Chlorophenyl)-2-cyano-6,6,6-trifluoro-3-
phenylhexa-2,4-dienamide (3k). Yield: 87%; yellow solid; mp:
170e171 ꢁC; IR (CH2Cl2, film): 3486, 3247, 2221,1700,1595,1492,1175,
4. (a) Dias, L. C.; Oliveira, L. G. Org. Lett. 2001, 3, 3951; (b) Jansen, R.; Kunze, B.;
€
Reichenbach, H.; Hofle, G. Eur. J. Org. Chem. 2000, 913; (c) Kunze, B.; Jansen, R.;
1030, 963 cmꢀ1
;
1H NMR (300 MHz, CDCl3):
d
¼7.88 (s, 1H), 7.26 (t,
€
Sasse, F.; Hofle, G.; Reichenbach, H. J. Antibiot. 1998, 51, 1075; (d) Erickson, K. L.;
Beutler, J. A.; Cardellina, J. H., II; Boyd, M. R. J. Org. Chem. 1997, 62, 8188; (e)
Tanaka, J.-I.; Higa, T. Tetrahedron Lett. 1996, 37, 5535.
J¼7.2 Hz, 2H), 7.16 (t, J¼7.5 Hz, 1H), 7.06e7.02 (m, 5H), 6.79 (d,
J¼8.4 Hz, 2H), 6.48 (s, 1H), 6.26 (s, 1H); 13C NMR (100 MHz, CDCl3):
163.0,162.2,136.9,136.4,135.4 (m, J¼30 Hz),134.6 (m, J¼6.5 Hz),130.7,
130.6, 130.0, 128.9, 128.3, 128.2, 122.7 (m, J¼270 Hz), 117.0, 108.1; 19F
5. (a) D’Souza, B. R.; Louie, J. Org. Lett. 2009, 11, 4168; (b) Oshita, M.; Yamashita,
K.; Tobisu, M.; Chatani, N. J. Am. Chem. Soc. 2005, 127, 761; (c) Li, Y.; Matsu-
mura, H.; Yamanaka, M.; Takahashi, T. Tetrahedron 2004, 60, 1393; (d) Pan, X.;
Cai, Q.; Ma, D. Org. Lett. 2004, 6, 1809; (e) Tanaka, R.; Hirano, S.; Urabe, H.;
Sato, F. Org. Lett. 2003, 5, 67; (f) Ma, S.; Xie, H. J. Org. Chem. 2002, 67, 6575; (g)
Takahashi, T.; Li, Y.; Tsai, F. Y.; Nakajima, K. Organometallics 2001, 20, 595; (h)
Abarbri, M.; Parrain, J. L.; Duchene, A. Synth. Commun. 1998, 28, 239; (i) Takai,
K.; Kataoka, Y.; Yoshizumi, K.; Oguchi, Y. Chem. Lett. 1991, 1479; (j) Williams,
A. C.; Sheffels, P.; Sheehan, D.; Livinghouse, T. Organometallics 1989, 8, 1566.
6. Babu, T. H.; Muralidharan, S. P. D.; Perumal, P. T. Synlett 2010, 2125.
NMR (CDCl3):
d
¼ꢀ65.8 (s, 3F); MS (ESI) (m/z): 399 (MþNaþ); HRMS
calcd for C19H12ClF3N2ONa: 399.0488, found: 399.0483.
4.2.12. (2E,4E)-5-(4-Bromophenyl)-2-cyano-6,6,6-trifluoro-3-
phenylhexa-2,4-dienamide (3l). Yield: 85%; yellow solid; mp: