A facile route to aryl amines: Nucleophilic substitution of aryl triflates

Synlett

Volumn , Issue 10, 1999, Pages 1559-1562

  Schio, Laurent ^a   Lemoine, Guy ^a   Klich, Michel ^a  

^a SANOFI   (France)

Author keywords

Amination; Aryl amine; Frontier orbitals; S(N)Ar; Triflate

Indexed keywords

AROMATIC AMINE; PYRIDINE DERIVATIVE;

AMINATION; ARTICLE; CHEMICAL REACTION KINETICS; MOLECULAR INTERACTION; SYNTHESIS;

EID: 0032825417     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1999-2886     Document Type: Article

References (25)

1. Ritter, K. Synthesis 1993, 735. For recent papers on cross-coupling reactions with various organometallic reagents, see for example: Baston, E.; Hartmann, R. W. Synth. Commun. 1998, 28, 2725; Olofsson, K.; Larhed, M.; Hallberg, A. J. Org. Chem. 1998, 63, 5076; Kamikawa, T.; Hayashi, T. Synlett 1997, 163; Badone, D.; Cardamone, R.; Guzzi, U. Tetrahedron Lett. 1994, 35, 5477; Quesnelle, C. A.; Familoni, O. B.; Snieckus, V. Synlett 1994, 349.
2. Ritter, K. Synthesis 1993, 735. For recent papers on cross-coupling reactions with various organometallic reagents, see for example: Baston, E.; Hartmann, R. W. Synth. Commun. 1998, 28, 2725; Olofsson, K.; Larhed, M.; Hallberg, A. J. Org. Chem. 1998, 63, 5076; Kamikawa, T.; Hayashi, T. Synlett 1997, 163; Badone, D.; Cardamone, R.; Guzzi, U. Tetrahedron Lett. 1994, 35, 5477; Quesnelle, C. A.; Familoni, O. B.; Snieckus, V. Synlett 1994, 349.
3. Ritter, K. Synthesis 1993, 735. For recent papers on cross-coupling reactions with various organometallic reagents, see for example: Baston, E.; Hartmann, R. W. Synth. Commun. 1998, 28, 2725; Olofsson, K.; Larhed, M.; Hallberg, A. J. Org. Chem. 1998, 63, 5076; Kamikawa, T.; Hayashi, T. Synlett 1997, 163; Badone, D.; Cardamone, R.; Guzzi, U. Tetrahedron Lett. 1994, 35, 5477; Quesnelle, C. A.; Familoni, O. B.; Snieckus, V. Synlett 1994, 349.
4. Ritter, K. Synthesis 1993, 735. For recent papers on cross-coupling reactions with various organometallic reagents, see for example: Baston, E.; Hartmann, R. W. Synth. Commun. 1998, 28, 2725; Olofsson, K.; Larhed, M.; Hallberg, A. J. Org. Chem. 1998, 63, 5076; Kamikawa, T.; Hayashi, T. Synlett 1997, 163; Badone, D.; Cardamone, R.; Guzzi, U. Tetrahedron Lett. 1994, 35, 5477; Quesnelle, C. A.; Familoni, O. B.; Snieckus, V. Synlett 1994, 349.
5. Ritter, K. Synthesis 1993, 735. For recent papers on cross-coupling reactions with various organometallic reagents, see for example: Baston, E.; Hartmann, R. W. Synth. Commun. 1998, 28, 2725; Olofsson, K.; Larhed, M.; Hallberg, A. J. Org. Chem. 1998, 63, 5076; Kamikawa, T.; Hayashi, T. Synlett 1997, 163; Badone, D.; Cardamone, R.; Guzzi, U. Tetrahedron Lett. 1994, 35, 5477; Quesnelle, C. A.; Familoni, O. B.; Snieckus, V. Synlett 1994, 349.
6. Ritter, K. Synthesis 1993, 735. For recent papers on cross-coupling reactions with various organometallic reagents, see for example: Baston, E.; Hartmann, R. W. Synth. Commun. 1998, 28, 2725; Olofsson, K.; Larhed, M.; Hallberg, A. J. Org. Chem. 1998, 63, 5076; Kamikawa, T.; Hayashi, T. Synlett 1997, 163; Badone, D.; Cardamone, R.; Guzzi, U. Tetrahedron Lett. 1994, 35, 5477; Quesnelle, C. A.; Familoni, O. B.; Snieckus, V. Synlett 1994, 349.
7. For excellent recent reviews see: Hartwig, J.F. Synlett 1997, 329; Hartwig, J. F. Angew. Chem. Int. Ed. Engl. 1998, 37, 2046; Frost, C.G.; Mendonca, P. J. Chem. Soc., Perkin Trans. 1 1998, 2615.
8. For excellent recent reviews see: Hartwig, J.F. Synlett 1997, 329; Hartwig, J. F. Angew. Chem. Int. Ed. Engl. 1998, 37, 2046; Frost, C.G.; Mendonca, P. J. Chem. Soc., Perkin Trans. 1 1998, 2615.
9. For excellent recent reviews see: Hartwig, J.F. Synlett 1997, 329; Hartwig, J. F. Angew. Chem. Int. Ed. Engl. 1998, 37, 2046; Frost, C.G.; Mendonca, P. J. Chem. Soc., Perkin Trans. 1 1998, 2615.
10. Kotsuki, H.; Kobayashi, S.; Suenaga, H.; Nishizawa, H. Synthesis 1990, 1145.
11. 2-aromatic triflates see: Chayer, S.; Essassi, E. M.; Bourguignon, J. J. Tetrahedron Lett. 1998, 39, 841; Cappelli, A.; Anzini, M.; Vomero, S.; Mennuni, L.; Makovec, F.; Doucet, E.; Hamon, M.; Bruni, G.; Romeo, M. R.; Menziani, M. C.; De Benedetti, P. G.; Langer, T. J. Med. Chem. 1998, 41, 728; Arcadi, A.; Cacchi, S.; Fabrizi, G.; Manna, F.; Pace, P. Synlett 1998, 446; Steinbrecher, T.; Wameling, C.; Oesch, F.; Seidel, A. Angew. Chem. Int. Ed. Engl. 1993, 32, 404; Megati, S.; Goren, Z.; Silverton, J. V.; Orlina, J.; Nishimura, H.; Shirasaki, T.; Mitsuya, H.; Zemlicka, J. J. Med. Chem. 1992, 35, 4098; Saari, W. S.; Halczenko, W.; King, S. W.; Huff, J. R.; Guare Jr, J. P.; Hunt, C. A.; Randall, W. C.; Anderson, P. S.; Lotti, V. J.; Taylor, D. A.; Clineschmidt, B. V. J. Med. Chem. 1983, 26, 1696.
12. 2-aromatic triflates see: Chayer, S.; Essassi, E. M.; Bourguignon, J. J. Tetrahedron Lett. 1998, 39, 841; Cappelli, A.; Anzini, M.; Vomero, S.; Mennuni, L.; Makovec, F.; Doucet, E.; Hamon, M.; Bruni, G.; Romeo, M. R.; Menziani, M. C.; De Benedetti, P. G.; Langer, T. J. Med. Chem. 1998, 41, 728; Arcadi, A.; Cacchi, S.; Fabrizi, G.; Manna, F.; Pace, P. Synlett 1998, 446; Steinbrecher, T.; Wameling, C.; Oesch, F.; Seidel, A. Angew. Chem. Int. Ed. Engl. 1993, 32, 404; Megati, S.; Goren, Z.; Silverton, J. V.; Orlina, J.; Nishimura, H.; Shirasaki, T.; Mitsuya, H.; Zemlicka, J. J. Med. Chem. 1992, 35, 4098; Saari, W. S.; Halczenko, W.; King, S. W.; Huff, J. R.; Guare Jr, J. P.; Hunt, C. A.; Randall, W. C.; Anderson, P. S.; Lotti, V. J.; Taylor, D. A.; Clineschmidt, B. V. J. Med. Chem. 1983, 26, 1696.
13. 2-aromatic triflates see: Chayer, S.; Essassi, E. M.; Bourguignon, J. J. Tetrahedron Lett. 1998, 39, 841; Cappelli, A.; Anzini, M.; Vomero, S.; Mennuni, L.; Makovec, F.; Doucet, E.; Hamon, M.; Bruni, G.; Romeo, M. R.; Menziani, M. C.; De Benedetti, P. G.; Langer, T. J. Med. Chem. 1998, 41, 728; Arcadi, A.; Cacchi, S.; Fabrizi, G.; Manna, F.; Pace, P. Synlett 1998, 446; Steinbrecher, T.; Wameling, C.; Oesch, F.; Seidel, A. Angew. Chem. Int. Ed. Engl. 1993, 32, 404; Megati, S.; Goren, Z.; Silverton, J. V.; Orlina, J.; Nishimura, H.; Shirasaki, T.; Mitsuya, H.; Zemlicka, J. J. Med. Chem. 1992, 35, 4098; Saari, W. S.; Halczenko, W.; King, S. W.; Huff, J. R.; Guare Jr, J. P.; Hunt, C. A.; Randall, W. C.; Anderson, P. S.; Lotti, V. J.; Taylor, D. A.; Clineschmidt, B. V. J. Med. Chem. 1983, 26, 1696.
14. 2-aromatic triflates see: Chayer, S.; Essassi, E. M.; Bourguignon, J. J. Tetrahedron Lett. 1998, 39, 841; Cappelli, A.; Anzini, M.; Vomero, S.; Mennuni, L.; Makovec, F.; Doucet, E.; Hamon, M.; Bruni, G.; Romeo, M. R.; Menziani, M. C.; De Benedetti, P. G.; Langer, T. J. Med. Chem. 1998, 41, 728; Arcadi, A.; Cacchi, S.; Fabrizi, G.; Manna, F.; Pace, P. Synlett 1998, 446; Steinbrecher, T.; Wameling, C.; Oesch, F.; Seidel, A. Angew. Chem. Int. Ed. Engl. 1993, 32, 404; Megati, S.; Goren, Z.; Silverton, J. V.; Orlina, J.; Nishimura, H.; Shirasaki, T.; Mitsuya, H.; Zemlicka, J. J. Med. Chem. 1992, 35, 4098; Saari, W. S.; Halczenko, W.; King, S. W.; Huff, J. R.; Guare Jr, J. P.; Hunt, C. A.; Randall, W. C.; Anderson, P. S.; Lotti, V. J.; Taylor, D. A.; Clineschmidt, B. V. J. Med. Chem. 1983, 26, 1696.
15. 2-aromatic triflates see: Chayer, S.; Essassi, E. M.; Bourguignon, J. J. Tetrahedron Lett. 1998, 39, 841; Cappelli, A.; Anzini, M.; Vomero, S.; Mennuni, L.; Makovec, F.; Doucet, E.; Hamon, M.; Bruni, G.; Romeo, M. R.; Menziani, M. C.; De Benedetti, P. G.; Langer, T. J. Med. Chem. 1998, 41, 728; Arcadi, A.; Cacchi, S.; Fabrizi, G.; Manna, F.; Pace, P. Synlett 1998, 446; Steinbrecher, T.; Wameling, C.; Oesch, F.; Seidel, A. Angew. Chem. Int. Ed. Engl. 1993, 32, 404; Megati, S.; Goren, Z.; Silverton, J. V.; Orlina, J.; Nishimura, H.; Shirasaki, T.; Mitsuya, H.; Zemlicka, J. J. Med. Chem. 1992, 35, 4098; Saari, W. S.; Halczenko, W.; King, S. W.; Huff, J. R.; Guare Jr, J. P.; Hunt, C. A.; Randall, W. C.; Anderson, P. S.; Lotti, V. J.; Taylor, D. A.; Clineschmidt, B. V. J. Med. Chem. 1983, 26, 1696.
16. 2-aromatic triflates see: Chayer, S.; Essassi, E. M.; Bourguignon, J. J. Tetrahedron Lett. 1998, 39, 841; Cappelli, A.; Anzini, M.; Vomero, S.; Mennuni, L.; Makovec, F.; Doucet, E.; Hamon, M.; Bruni, G.; Romeo, M. R.; Menziani, M. C.; De Benedetti, P. G.; Langer, T. J. Med. Chem. 1998, 41, 728; Arcadi, A.; Cacchi, S.; Fabrizi, G.; Manna, F.; Pace, P. Synlett 1998, 446; Steinbrecher, T.; Wameling, C.; Oesch, F.; Seidel, A. Angew. Chem. Int. Ed. Engl. 1993, 32, 404; Megati, S.; Goren, Z.; Silverton, J. V.; Orlina, J.; Nishimura, H.; Shirasaki, T.; Mitsuya, H.; Zemlicka, J. J. Med. Chem. 1992, 35, 4098; Saari, W. S.; Halczenko, W.; King, S. W.; Huff, J. R.; Guare Jr, J. P.; Hunt, C. A.; Randall, W. C.; Anderson, P. S.; Lotti, V. J.; Taylor, D. A.; Clineschmidt, B. V. J. Med. Chem. 1983, 26, 1696.
17. 3, ppm): δ 7.80, 7.43 (4H, AA'BB' system). Analyses for the elements C, H, F, N, S were within ± 0.2% of theoretical values.
18. For a comprehensive textbook on frontier orbital theory, see: Fleming, I. in Frontier Orbitals and Organic Chemical Reactions, Wiley, London, 1976. For a discussion on aromatic nucleophilic substitution with aryl halides see chapter 3, 68-69 and references cited therein.
19. Low energy conformations were identified using force field calculations (in-house software). Following MNDO or CNINDO/2 calculations (programmes implemented in QCPE package), relevant frontier orbitals were assigned based on electronic density at the reaction site.
20. Only triflates reacting cleanly (yield > 70%) were considered. Amination reactions were performed at 25°C using a thermostated water bath. Product formation and triflate consumption were followed by HPLC.
21. HOMO octylamine = -10.435 eV
22. Prepared according to the following Scheme: (Formula Presented)
23. 1c = 0.0799 eV.
24. Takemura, S.; Miki, Y.; Uono, M.; Yoshimura, K.; Kuroda, M.; Suzuki, A. Chem. Pharm. Bull. 1981, 29, 3026.
25. +, 25), 575 (12), 422 (75), 167 (100), 73 (12).