Organic Letters
Letter
(10) Although several rare-earth metal triflates were briefly examined
for direct catalytic amidation of esters,5h those catalysts were less
effective than zirconium-based catalysts and not fully examined in
detail.
Synthetic Organic Chemistry, Japan and Y.S. thanks JSPS
Research Fellowships for Young Scientists. We thank the
research group of Prof. Hiroshi Suemune at Kyushu University
for the use of a polarimeter.
(11) The reaction did not proceed well in the presence of catalytic
amounts of TfOH (4% after 24 h).8
REFERENCES
(12) p-TsNH2 and H2NOH·HCl with Et3N did not provide
amidation products under our catalytic conditions.
(13) For related examples with α-amino acids using B(OCH2CF3)3
as a stoichiometric reagent, see: Lanigan, R. M.; Starkov, P.; Sheppard,
T. D. J. Org. Chem. 2013, 78, 4512.
■
(1) Recent reviews on the synthesis of amides: (a) Stolze, S. C.;
Kaiser, M. Synthesis 2012, 44, 1755. (b) El-Faham, A.; Albericio, F.
Chem. Rev. 2011, 111, 6557. (c) Pattabiraman, V. R.; Bode, J. W.
Nature 2011, 480, 471. (d) Allen, C. L.; Williams, J. M. J. Chem. Soc.
Rev. 2011, 40, 3405. For the importance of amidation reactions, see:
(e) Constable, D. J. C.; Dunn, P. J.; Hayler, J. D.; Humphrey, G. R.;
Leazer, J. J. L.; Linderman, R. J.; Lorenz, K.; Manley, J.; Pearlman, B.
A.; Wells, A.; Zaks, A.; Zhang, T. Y. Green Chem. 2007, 9, 411.
(2) For a review, see: (a) Lanigan, R. M.; Sheppard, T. D. Eur. J. Org.
Chem. 2013, 7453. For selected recent examples of catalytic direct
amidation of carboxylic acids, see: (b) Yamashita, R.; Sakakura, A.;
Ishihara, K. Org. Lett. 2013, 15, 3654. (c) Gernigon, N.; Al-Zoubi, R.
M.; Hall, D. G. J. Org. Chem. 2012, 77, 8386. (d) Lundberg, H.; Tinnis,
F.; Adolfsson, H. Chem.Eur. J. 2012, 18, 3822. (e) Allen, C. L.;
Chhatwal, A. R.; Williams, J. M. J. Chem. Commun. 2012, 48, 666.
(f) Arnold, K.; Batsanov, A. S.; Davies, B.; Whiting, A. Green Chem.
2008, 10, 124.
(14) For example, see: (a) Zaitsev, V. G.; Shabashov, D.; Daugulis, O.
J. Am. Chem. Soc. 2005, 127, 13154. (b) Gou, F.-R.; Wang, X.-C.; Huo,
P.-F.; Bi, H.-P.; Guan, Z.-H.; Liang, Y.-M. Org. Lett. 2009, 11, 5726.
(c) Zhao, Y.; Chen, G. Org. Lett. 2011, 13, 4850. (d) He, G.; Chen, G.
Angew. Chem., Int. Ed. 2011, 50, 5192. (e) He, G.; Zhao, Y.; Zhang, S.;
Lu, C.; Chen, G. J. Am. Chem. Soc. 2012, 134, 3. (f) Nadres, E. T.;
Daugulis, O. J. Am. Chem. Soc. 2012, 134, 7. (g) Zhang, S.-Y.; He, G.;
Zhao, Y.; Wright, K.; Nack, W. A.; Chen, G. J. Am. Chem. Soc. 2012,
134, 7313. (h) He, G.; Lu, C.; Zhao, Y.; Nack, W. A.; Chen, G. Org.
Lett. 2012, 14, 2944. (i) Zhao, Y.; He, G.; Nack, W. A.; Chen, G. Org.
Lett. 2012, 14, 2948. (j) Zhang, S.-Y.; He, G.; Nack, W. A.; Zhao, Y.;
Li, Q.; Chen, G. J. Am. Chem. Soc. 2013, 135, 2124. (k) Hack, W. A.;
He, G.; Zhang, S.-Y.; Lu, C.; Chen, G. Org. Lett. 2013, 15, 3440.
(l) Sustac Roman, D.; Charette, A. B. Org. Lett. 2013, 15, 4394.
(m) Nadres, E. T.; Franco Santos, G. I.; Shabashov, D.; Daugulis, O. J.
Org. Chem. 2013, 78, 9689.
(15) For example, see: (a) Hayashi, Y.; Santoro, S.; Azuma, Y.; Himo,
F.; Ohshima, T.; Mashima, K. J. Am. Chem. Soc. 2013, 135, 6192.
(b) Ohshima, T.; Iwasaki, T.; Maegawa, Y.; Yoshiyama, A.; Mashima,
K. J. Am. Chem. Soc. 2008, 130, 2944. (c) Uesugi, S.; Li, Z.; Yazaki, R.;
Ohshima, T. Angew. Chem., Int. Ed. 2014, 53, 1611.
(16) Limited conversion for 1s and 1t in the absence of the catalyst
would be due to the formation of HCl during the reaction that reduces
the nucleophilicity of amine 2a.
(17) (a) Trost, B. M.; Hachiya, I. J. Am. Chem. Soc. 1998, 120, 1104.
(b) Barnes, D. J.; Chapman, R. L.; Vagg, R. S.; Watton, E. C. J. Chem.
Eng. Data 1978, 23, 349. (c) Conlon, D. A.; Yasuda, N. Adv. Synth.
Catal. 2001, 343, 137.
(18) Thalji, R. K.; McAtee, J. J.; Belyanskaya, S.; Brandt, M.; Brown,
G. D.; Costell, M. H.; Ding, Y.; Dodson, J. W.; Eisennagel, S. H.; Fries,
R. E.; Gross, J. W.; Harpel, M. R.; Holt, D. A.; Israel, D. I.; Jolivette, L.
J.; Krosky, D.; Li, H.; Lu, Q.; Mandichak, T.; Roethke, T.;
Schnackenberg, C. G.; Schwartz, B.; Shewchuk, L. M.; Xie, W.;
Behm, D. J.; Douglas, S. A.; Shaw, A. L.; Marino, J. P., Jr. Bioorg. Med.
Chem. Lett. 2013, 23, 3584.
(3) For recent analysis, see: (a) Roughley, S. D.; Jordan, A. M. J. Med.
Chem. 2011, 54, 3451. (b) Carey, J. S.; Laffan, D.; Thomson, C.;
Williams, M. T. Org. Biomol. Chem. 2006, 4, 2337.
(4) For example, see: (a) Basha, A.; Lipton, M.; Weinreb, S. M.
Tetrahedron Lett. 1977, 4171. (b) Lipton, M. F.; Basha, A.; Weinreb, S.
M. Org. Synth. 1979, 59, 49. (c) Ishihara, K.; Kuroki, Y.; Hanaki, N.;
Ohara, S.; Yamamoto, H. J. Am. Chem. Soc. 1996, 118, 1569.
(5) For selected recent examples of catalytic direct amidation of
esters, see: (a) Caldwell, N.; Jamieson, C.; Simpson, I.; Watson, A. J. B.
ACS Sustainable Chem. Eng. 2013, 1, 1339. (b) Caldwell, N.; Jamieson,
C.; Simpson, I.; Tuttle, T. Org. Lett. 2013, 15, 2506. (c) Ohshima, T.;
Hayashi, Y.; Agura, K.; Fujii, Y.; Yoshiyama, A.; Mashima, K. Chem.
Commun. 2012, 48, 5434. (d) Whitten, K. M.; Makriyannis, A.;
Vadivel, S. K. Tetrahedron Lett. 2012, 53, 5753. (e) Price, K. E.;
́
Larriveee-Aboussafy, C.; Lillie, B. M.; McLaughlin, R. W.; Mustakis, J.;
Hettenbach, K. W.; Hawkins, J. M.; Vaidyanathan, R. Org. Lett. 2009,
11, 2003. (f) Yang, X.; Birman, V. B. Org. Lett. 2009, 11, 1499.
(g) Sabot, C.; Kumar, K. A.; Meunier, S.; Mioskowski, C. Tetrahedron
Lett. 2007, 48, 3863. (h) Han, C.; Lee, J. P.; Lobkovsky, E.; Porco, J.
A., Jr. J. Am. Chem. Soc. 2005, 127, 10039. (i) Movassaghi, M.;
Schmidt, M. A. Org. Lett. 2005, 7, 2453.
(6) For selected other approaches toward environmentally benign
amide formation reactions, see: (a) Gunanathan, C.; Ben-David, Y.;
Milstein, D. Science 2007, 317, 790. (b) Gnanaprakasam, B.; Milstein,
́
D. J. Am. Chem. Soc. 2011, 133, 1682. (c) Soule, J.-F.; Miyamura, H.;
Kobayashi, S. J. Am. Chem. Soc. 2011, 133, 18550. (d) Kang, B.; Fu, Z.;
Hong, S. H. J. Am. Chem. Soc. 2013, 135, 11704.
(7) Shimizu, Y.; Morimoto, H.; Zhang, M.; Ohshima, T. Angew.
Chem., Int. Ed. 2012, 51, 8564.
(8) See the Supporting Information for details.
(9) For reviews of rare-earth metal catalysts, see: (a) Shibasaki, M.;
Matsunaga, S.; Kumagai, N. In Acid Catalysis in Modern Organic
Synthesis; Yamamoto, H., Ishihara, K., Eds.; Wiley-VCH: Weinheim,
2008; Vol. 2, Chapter 13. (b) Kobayashi, S.; Sugiura, M.; Kitagawa, H.;
Lam, W. W.-L. Chem. Rev. 2002, 102, 2227. For recent examples of
the use of lanthanum and other rare-earth metal salts as catalyst in
related transformations, see: (c) Hatano, M.; Ishihara, K. Chem.
Commun. 2013, 49, 1983 and references therein. (d) Hatano, M.;
Furuya, Y.; Shimmura, T.; Moriyama, K.; Kamiya, S.; Maki, T.;
Ishihara, K. Org. Lett. 2011, 13, 426. (e) Distaso, M.; Quaranta, E.
Tetrahedron 2004, 60, 1531. (f) Distaso, M.; Quaranta, E. J. Catal.
2004, 228, 36. (g) Brown, R. S.; Neverov, A. A.; Tsang, J. S. W.;
Gibson, G. T. T.; Montoya-Pelaez, P. J. Can. J. Chem. 2004, 82, 1791.
(h) Neverov, A. A.; McDonald, T.; Gibson, G.; Brown, R. S. Can. J.
Chem. 2001, 79, 1704. See also ref 5h.
D
dx.doi.org/10.1021/ol500593v | Org. Lett. XXXX, XXX, XXX−XXX