1470
B. Miriyala et al. / Tetrahedron 60 (2004) 1463–1471
M. V.; Khidekel, M. L. Russ. Chem. Rev. 1980, 49, 14.
(c) Tarasevich, V. A.; Kozlov, N. G. Russ. Chem. Rev. 1999,
68, 55. A modification of Leuckart’s synthesis of primary
amines from ketones using HCOONH4 and Pd–C has been
reported recently: (d) Allegretti, M.; Berdini, V.; Candida
Cesra, M.; Curti, R.; Nicolini, L.; Topai, A. Tetrahedron Lett.
2001, 42, 4257. (e) Gross, T.; Seayad, A. M.; Ahmad, M.;
Beller, M. Org. Lett. 2002, 4, 2055, and references cited
therein.
4H), 3.79 (s, 4H); EIMS: 410.6 (MþH, calcd for
C28H27NO2, 410.53).
4.2.11. Bis-(indol-3-ylmethyl)amine22h (31). Yield 65%;
IR: 3409, 3054, 2794, 1556, 1456, 1421, 1338, 125, 1092,
1
1009, 741 cm21; H NMR: d 10.85 (s, 2H), 7.49–7.47 (d,
J¼8 Hz, 2H), 7.32–7.30 (d, J¼8 Hz, 2H), 7.26 (s, 2H), 7.1–
6.9 (m, 2H), 6.88–6.85 (m, 2H), 3.67 (s, 4H); EIMS: 276.3
(MþH, calcd for C18H17N3, 276.35).
5. (a) Borch, R. F.; Durst, H. D. J. Am. Chem. Soc. 1969, 91,
3996. (b) Borch, R. F.; Bernstein, M. D.; Durst, H. D. J. Am.
Chem. Soc. 1971, 93, 2897. (c) Mattson, R. J.; Pham, K. M.;
Leuck, D. J.; Cowen, K. A. J. Org. Chem. 1990, 55, 2552.
6. Abdel-Magid, A. F.; Carson, K. G.; Harris, B. D.; Maryanoff,
C. A.; Shah, R. D. J. Org. Chem. 1996, 61, 3849.
4.2.12. Bis-(2-phenylpropyl)amine22i (32). Yield 58%; IR:
3297, 3027, 2961, 1601, 1493, 1452, 1228, 1129, 761,
1
700 cm21; H NMR: d 7.35–7.09 (m, 10H), 2.9–2.86 (m,
2H), 2.82–2.67 (m, 4H), 1.2–1.18 (2d, J¼4 Hz, 6H); EIMS:
254.3 (MþH, calcd for C18H23N, 254.39.
7. (a) Pelter, A.; Rosser, R. M.; Mills, S. J. Chem. Soc. Perkin
Trans. 1 1984, 717. (b) Bomann, M. D.; Guch, I. C.; Dimare,
M. J. Org. Chem. 1995, 60, 5995.
4.2.13. Bis-(3-phenylpropyl)amine22i (33). Yield 75%; 1H
NMR: d 7.38–7.06 (m, 10H), 3.5 (t, 1H, J¼6.0 Hz), 3.0–
2.3 (m, 6H), 2.2–1.5 (m, 6H); EIMS: 254.5 (MþH, calcd
for C18H23N, 254.39.
8. (a) Bhattacharyya, S.; Chatterjee, A.; Duttachowdhury, S. K.
J. Chem. Soc. Perkin Trans. 1 1994, 1. (b) Ranu, B. C.; Majee,
A.; Sarkar, A. J. Org. Chem. 1998, 63, 370.
4.2.14. Bis-(cyclohexylmethyl)amine (34). Yield 68%; 1H
NMR: d 2.43 (d, 4H, J¼6.0 Hz), 1.85–1.62 (m, 11H), 1.55–
1.4 (m, 4H), 1.35–1.1 (m, 8H); EIMS: 211.5 (MþH, calcd
for C14H27N, 210.37.
9. See, for example: (a) Saxena, I.; Borah, R.; Sarma, J. C.
J. Chem. Soc. Perkin Trans. 1 2000, 503. (b) Bhattacharyya, S.
Synth. Commun. 1997, 27, 4265.
10. (a) Han, Y.; Chorev, M. J. Org. Chem. 1999, 64, 1972.
(b) Chandrasekhar, S.; Reddy, C. R.; Ahmed, M. Synlett 2000,
1655. (c) Chen, B. C.; Sundeen, J. E.; Guo, P.; Bednarz, M. S.;
Zhao, R. Tetrahedron Lett. 2001, 42, 1245. (d) Apodaca, R.;
Xiao, W. Org. Lett. 2001, 3, 1745.
References and notes
11. See, for example: (a) Suwa, T.; Shibata, I.; Nishino, K.; Baba,
A. Org. Lett. 1999, 1, 1579. (b) Suwa, T.; Sugiyama, E.;
Shibata, I.; Baba, A. Synthesis 2000, 789.
1. For some leading references, see: (a) Manchand, P. S.; Cerruti,
R. L.; Martin, J. A.; Hill, C. H.; Merrett, J. H.; Keech, E.;
Belshe, R. B.; Connell, E. V.; Sim, I. S. J. Med. Chem. 1990,
33, 1992. (b) Askin, D.; Wallace, M. A.; Vacca, J. P.; Reamer,
R. A.; Volante, R. P.; Shinkai, I. J. Org. Chem. 1992, 57, 2771.
(c) Main, B. G.; Tucker, H. Medicinal chemistry; Genellin,
C. R., Roberts, S. M., Eds.; Academic: New York, 1993; 2nd
ed., p 187. (d) Gallop, M. A.; Barrett, R. W.; Dower, W. J.;
Fodor, S. P. A.; Gordon, E. M. J. Med. Chem. 1994, 37, 1233.
(e) Gordon, E. M.; Barrett, R. W.; Dower, W. J.; Fodor, S. P.
A.; Gallop, M. A. J. Med. Chem. 1994, 37, 1385. (f) Bergeron,
R. J.; Feng, Y.; Weimer, W. R.; McManis, J. S.; Dimova, H.;
Porter, C.; Raisler, B.; Phansitiel, O. J. Med. Chem. 1997, 40,
1475. (g) Kuksa, V.; Buchan, R.; Lin, P. K. T. Synthesis 2000,
1189. (h) Karigiannis, G.; Papaioannou, D. Eur. J. Org. Chem.
2000, 1841. (i) Merla, B.; Risch, N. Synthesis 2002, 1365.
2. (a) Ghose, A. K.; Viswanadhan, V. N.; Wendoloski, J. J.
J. Comb. Chem. 1999, 1, 55. (b) Henkel, T.; Brunne, R. M.;
Mueller, H.; Reichel, F. Angew. Chem. Int. Ed. Engl. 1999, 38,
643.
12. Itoh, T.; Nagata, K.; Kurihara, A.; Miyazaki, M.; Ohsawa, A.
Tetrahedron Lett. 2002, 43, 3105.
13. (a) Smith, M. B.; March, J. March’s advanced organic
chemistry; Wiley: New York, 2001; p 1187 and references
cited therein. (b) Also see, Ref. 3g, pp 28, 31.
14. (a) Soroka, M.; Zygmunt, J. Synthesis 1988, 370. (b) Purchase,
C. F.; Goel, O. P. J. Org. Chem. 1991, 56, 457. (c) Sharma,
S. K.; Songster, M. F.; Colpitts, T. L.; Hegyes, P.; Barany, G.;
Castellino, F. J. J. Org. Chem. 1993, 58, 4993. (d) Helion-
Garro, F.; Merzouk, A.; Guibe, F. J. Org. Chem. 1993, 58,
6109. (e) Dube, D.; Scholte, A. A. Tetrahedron Lett. 1999, 40,
2295. (f) Bernacka, E.; Klepacz, A.; Zwierzak, A. Tetrahedron
Lett. 2001, 42, 5093. (g) Mukade, T.; Dragoli, D. R.; Ellman,
J. A. J. Comb. Chem. 2003, 5, 590, and references therein.
15. For examples, see: (a) Bhattacharyya, S. Tetrahedron Lett.
1994, 35, 2401. (b) Bhattacharyya, S. Synlett 1994, 1029.
(c) Bhattacharyya, S. J. Org. Chem. 1995, 60, 4928.
(d) Bhattacharyya, S.; Chatterjee, A.; Williamson, J. S. Synlett
1995, 1079. (e) Neidigh, K. A.; Avery, M. A.; Williamson,
J. S.; Bhattacharyya, S. J. Chem Soc. Perkin Trans. 1 1998,
2527.
3. For reviews on reductive aminations see: (a) Emerson, W. S.
Organic reactions; Wiley: New York, 1948; Vol. 4. p 174.
(b) Moore, M. L. Organic reactions; Wiley: New York, 1949;
Vol. 5. p 301. (c) Lane, C. F. Synthesis 1975, 135. (d) Hutchins,
R. O.; Natale, N. Org. Prep. Proced. Int. 1979, 11, 201.
(e) Gribble, G. W.; Nutaitis, C. F. Org. Prep. Proced. Int.
1985, 17, 317. (f) Hutchins, R. O.; Hutchins, M. K.
Comprehensive organic synthesis; Trost, B. M., Fleming, I.,
Eds.; Pergamon: Oxford, 1991; Vol. 8, p 25. (g) Baxter, E. W.;
Reitz, A. B. Organic reactions; Wiley: New York, 2002; Vol.
59. p 1.
16. In addition to our efforts, a few other reductive amination
protocols using Ti(OiPr)4 and borohydride-based reducing
agents have been described: See, for example, Refs. 5c,6, and
Breitenbucher, J. G.; Hui, H. C. Tetrahedron Lett. 1998, 39,
8207. Another modification using polymethylhydrosiloxane as
the reducing agent (Ref. 10b) has appeared recently, although
no references to prior work was cited.
17. A part of this work has been published in a preliminary
communication: Bhattacharyya, S.; Neidigh, K. A.; Avery,
M. A.; Williamson, J. S. Synlett 1999, 1781.
4. (a) Rylander, P. N. Catalytic hydrogenation in organic
synthesis; Academic: New York, 1979; p 165. (b) Klyuev,