11134
Y. Saito et al. / Tetrahedron 64 (2008) 11129–11135
4.6. General procedure for carboxamidation of 3-(2-
furyl)acrylic acid (10) or trans-cinnamic acid (1c) with
amino acid ester hydrochloride 11 using BBDI (Table 5)
4.7. Catalytic carboxamidation of 3-phenylpropanoic acid (1a)
with benzylamine (2a) using BBDI (Table 6)
a-
A mixture of 1a (1 mmol) and a combination of Boc2O and BBDI
of amounts shown in Table 6 in CH2Cl2 (2 mL) was stirred in con-
ditions described in Table 6. After addition of 2a (1.2 mmol) to the
mixture, the whole was stirred in conditions described in Table 6.
Ethyl acetate (40 mL) was added to the reaction mixture and then
the whole was successively washed with 5% HCl solution
(10 mLꢀ2) and brine (10 mL), dried (MgSO4), and concentrated
under reduced pressure. The residue was purified by flash column
chromatography on silica gel to give 3a and 15 in yields shown in
Table 6.
A mixture of 10 or 1c (1.1 mmol) and BBDI (1.05 mmol) in CH2Cl2
(3 mL) was stirred at room temperature for 1 h. After addition of
hydrochloride salt 11 (1.05 mmol) to the mixture, the whole was
stirred at room temperature for 24 h. Ethyl acetate (40 mL) was
added to the reaction mixture and then the whole was successively
washed with 5% HCl solution (10 mLꢀ2), 10% K2CO3 (10 mLꢀ2), and
brine (10 mL), dried (MgSO4), and concentrated under reduced
pressure. The residue was purified by flash column chromatogra-
phy on silica gel to give 12a–f in yields shown in Table 5.
4.6.1. Furylacryloyl-methionine methyl ester (12a)
Acknowledgements
26
Pale yellow needles. Mp 101–102 ꢁC [lit.14 mp 103 ꢁC]. [
a]
D
þ22.6 (c 1.2, CHCl3). IR (KBr) cmꢂ1: 1228, 1616, 1741, 3274. 1H NMR
We are grateful for the financial supports provided by a Grant-
in-Aid for Young Scientists (B) (No. 20790104) from Japan Society
for the Promotion of Science (JSPS) to Y.S. and High Technology
Research Program from Ministry of Education, Culture, Sports,
Sciences and Technology (MEXT), Japan.
(270 MHz, CDCl3): d 1.98–2.11 (m, 4H), 2.17–2.30 (m, 1H), 2.49–2.58
(m, 2H), 3.78 (s, 3H), 4.82–4.90 (m, 1H), 6.37 (d, J¼15.3 Hz, 1H),
6.44–6.46 (m, 2H), 6.55–6.59 (m, 1H), 7.41 (d, J¼15.7 Hz, 1H), 7.44
(m, 1H). MS (EI) m/z 283 (Mþ).
4.6.2. Furylacryloyl-valine methyl ester (12b)
References and notes
27
Pale yellow needles. Mp 159–160 ꢁC [lit.14 mp 146 ꢁC]. [
a]
D
þ45.4 (c 1.2, CHCl3). IR (KBr) cmꢂ1: 1216, 1536, 1563, 1618, 1735,
1. Beckwith, A. L. J. In The Chemistry of Amides; Zabicky, J., Ed.; Intersciences:
London, 1970.
3290. 1H NMR (270 MHz, CDCl3):
d 0.88–0.99 (m, 6H), 2.16–2.28 (m,
2. (a) Benz, G. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.;
Pergamon: Oxford, 1991; Vol. 6, pp 381–417; (b) Klausner, Y. S.; Bodansky, M.
Synthesis 1972, 453–463; (c) Challis, B. C.; Challis, J. A. In Comprehensive Organic
Chemistry; Barton, D. H. R., Ollis, W. D., Eds.; Pergamon: Oxford, 1979; Vol. 2,
p 957; (d) Sandler, S. R.; Karo, W. In Organic Functional Group Preparations, 2nd
ed.; Wasserman, H. H., Ed.; Academic: New York, NY, 1983; Vol. 1, p 315; (e)
Bailey, P. D.; Collier, I. D.; Morgan, K. M. In Comprehensive Organic Functional
Groups Transformations; Katrizky, A. L., Meth-Cohn, O., Rees, C. W., Eds.; Per-
gamon: New York, NY, 1995; Vol. 5, p 257; (f) Handbook of Reagents for Organic
Synthesis, Reagents for Glycoside, Nucleotide, and Peptide Synthesis; Crich, D., Ed.;
John Wiley & Sons: West Sussex, 2005.
3. For a recent review: Tanabe, Y.; Misaki, T.; Iida, A.; Nishii, Y. Yuki Gosei Kagaku
Kyokaishi 2004, 62, 1249–1259.
4. (a) Kunishima, M.; Kawachi, C.; Iwasaki, F.; Terao, K.; Tani, S. Tetrahedron Lett.
1999, 40, 5327–5330; (b) Arnold, K.; Davies, B.; Herault, D.; Whiting, A. Angew.
Chem., Int. Ed. 2008, 47, 2673–2676.
1H), 3.67 (s, 3H), 4.70–4.75 (m, 1H), 6.35 (br s, 1H), 6.42 (d,
J¼14.8 Hz, 1H), 6.42–6.45 (m, 1H), 6.54 (m, 1H), 7.42 (d, J¼15.3 Hz,
1H), 7.43 (m, 1H). MS (EI) m/z 251 (Mþ). HRMS Calcd for C13H17NO4
(Mþ): 251.1158. Found: 251.1161.
4.6.3. Furylacryloyl-phenylalanine methyl ester (12c)
26
Pale yellow needles. Mp 103 ꢁC [lit.14 mp 109 ꢁC]. [
a]
þ173.4 (c
D
0.7, CHCl3). IR (KBr) cmꢂ1: 1539, 1565, 1619, 1655, 1732, 3311. 1H
NMR (270 MHz, CDCl3): 3.11–3.26 (m, 2H), 3.77 (s, 3H), 4.99–5.06
d
(m, 1H), 6.16 (br s, 1H), 6.31 (d, J¼15.3 Hz, 1H), 6.43–6.45 (m, 1H),
6.54–6.55 (m, 1H), 7.09–7.12 (m, 2H), 7.21–7.31 (m, 3H), 7.41 (d,
J¼15.2 Hz, 1H), 7.42 (m, 1H). MS (EI) m/z 299 (Mþ). HRMS Calcd for
C17H17NO4 (Mþ): 299.1158. Found: 299.1157.
5. Catalytic amide condensation has been little known, but Yamamoto et al. re-
cently reported boronic acid-catalyzed amide condensation. Maki, T.; Ishihara,
K.; Yamamoto, H. Tetrahedron 2007, 63, 8645–8657.
6. (a) Saito, Y.; Ouchi, H.; Takahata, H. Tetrahedron 2006, 62, 11599–11607; (b)
Ouchi, H.; Saito, Y.; Yamamoto, Y.; Takahata, H. Org. Lett. 2002, 4, 585–587.
7. (a) Saito, Y.; Yamaki, T.; Kohashi, F.; Watanabe, T.; Ouchi, H.; Takahata, H. Tet-
rahedron Lett. 2005, 46, 1277–1279; (b) Saito, Y.; Watanabe, T.; Takahata, H.
Tetrahedron Lett. 2006, 47, 3099–3102.
4.6.4. Furylacryloyl-tyrosine methyl ester (12d)
Colorless prisms. Mp 135–137 ꢁC [lit.14 mp 90 ꢁC]. [ 26 –73.0 (c
a]
D
0.9, MeOH). 1H NMR (270 MHz, CDCl3):
d 3.01–3.17 (m, 2H), 3.74 (s,
3H), 4.95–5.01 (m, 1H), 6.20 (br d, J¼7.9 Hz, 1H), 6.30 (d, J¼15.3 Hz,
1H), 6.42–6.45 (m, 1H), 6.54 (d, J¼3.3 Hz, 1H), 6.58 (s, 1H), 6.73 (d,
J¼8.6 Hz, 2H), 6.95 (d, J¼8.6 Hz, 2H), 7.40 (d, J¼17.9 Hz, 1H), 7.42 (s,
1H). MS (EI) m/z 315 (Mþ). Anal. Calcd for C17H17NO5: C, 64.75; H,
5.43; N, 4.44. Found: C, 64.55; H, 5.26; N, 4.39.
8. Belleau, B.; Malek, G. J. Am. Chem. Soc. 1968, 90, 1651.
9. Kiso, Y.; Yajima, H. J. Chem. Soc., Chem. Commun. 1972, 942–943.
10. Recently, it was reported the use of these reagents resulted in low yields in
amidation of secondary amine with carboxylic acid. Valeur, E.; Bradley, M.
Tetrahedron 2007, 63, 8855–8871.
11. Kiuchi, F.; Nakamura, N.; Tsuda, Y.; Kondo, K.; Yoshimura, H. Chem. Pharm. Bull.
1988, 36, 2452–2465.
4.6.5. trans-Cinnamoyl-methionine methyl ester (12e)
12. (a) Parmar, V. S.; Jain, S. C.; Bisht, K. S.; Jain, R.; Taneja, P.; Jha, A.; Tyagi, O. D.;
Prasad, A. K.; Wengel, J.; Olsen, C. E.; Boll, P. M. Phytochemistry 1999, 46, 597–
673; (b) Kumar, S.; Singhal, V.; Roshan, R.; Sharma, A.; Rembhotkar, G. W.;
Ghosh, B. Eur. J. Pharmacol. 2007, 575, 177–186.
27
Colorless needles. Mp 87–88 ꢁC [lit.14 mp 137 ꢁC]. [
a]
þ43.9 (c
D
1.4, CHCl3). 1H NMR (270 MHz, CDCl3):
d 1.98–2.14 (m, 4H), 2.17–
2.34 (m, 1H), 2.57 (t, J¼7.6 Hz, 2H), 3.76 (s, 3H), 4.85–4.92 (m, 1H),
6.49 (d, J¼15.6 Hz, 1H), 6.75 (br s, 1H), 7.29–7.40 (m, 3H), 7.46–7.54
(m, 2H), 7.62 (d, J¼15.6 Hz, 1H). MS (EI) m/z 293 (Mþ). Anal. Calcd
for C15H19NO3S: C, 61.41; H, 6.53; N, 4.77. Found: C, 61.18; H, 6.47; N,
4.75.
13. Optical purities were determined by comparisons of optical rotations and HPLC
analyses. See Experimental section Brunel, J. M.; Salmi, C.; Letourneux, Y. Tet-
rahedron Lett. 2005, 46, 217–220.
14. (a) Dourtoglou, V.; Ziegler, J. C.; Gross, B. Tetrahedron Lett. 1978, 19, 1269–1272;
(b) Dourtoglou, V.; Ziegler, J. C.; Gross, B. Synthesis 1984, 572–574.
15. (a) Castro, B.; Dormoy, J. R.; Evin, G.; Selve, C. Tetrahedron Lett. 1975, 16, 1219–
1222; (b) Le-Nguyen, D.; Heitz, A.; Castro, B. J. Chem. Soc., Perkin Trans. 1 1987,
1915–1919; (c) Ward, D. E.; Gai, Y.; Lazny, R.; Pedras, M. S. C. J. Org. Chem. 2001,
66, 7832–7840.
16. Perreux, L.; Loupy, A.; Volatron, F. Tetrahedron 2002, 58, 2155–2162.
17. Ballini, R.; Bosica, G.; Fiorini, D. Tetrahedron 2003, 59, 1143–1145.
18. Barton, D. H. R.; Ferreira, J. A. Tetrahedron 1996, 52, 9347–9366.
19. Foot, J. S.; Kanno, H.; Giblin, G. M.; Taylor, R. J. K. Synthesis 2003, 1055–1064.
20. Petricci, E.; Botta, M.; Corelli, F.; Mugnaini, C. Tetrahedron Lett. 2002, 43,
6507–6509.
21. Zradni, F.-Z.; Hamelin, J.; Derdour, A. Synth. Commun. 2002, 32, 3525–3531.
22. Matsuda, F.; Itoh, S.; Hattori, N.; Yanagiya, M.; Matsumoto, T. Tetrahedron 1985,
41, 3625–3631.
4.6.6. trans-Cinnamoyl-valine methyl ester (12f)
Colorless prisms. Mp 130 ꢁC [lit.14 130 ꢁC]. [
a
]
þ44.5 (c 1.3,
26
D
CHCl3). IR (KBr) cmꢂ1: 1212, 1533, 1620, 1655, 1742, 2964, 3323. 1H
NMR (270 MHz, CDCl3):
d
0.97 (dd, J¼6.9, 8.4 Hz, 6H), 2.17–2.29 (m,
1H), 3.79 (s, 3H), 4.71–4.76 (m, 1H), 6.17 (br d, J¼8.6 Hz,1H), 6.48 (d,
J¼15.5 Hz, 1H), 7.33–7.39 (m, 3H), 7.48–7.53 (m, 2H) 7.64 (d,
J¼15.5 Hz, 1H). MS (EI) m/z 261 (Mþ). Anal. Calcd for C15H19NO3: C,
68.94; H, 7.33; N, 5.36. Found: C, 69.06; H, 7.32; N, 5.31.