Superacid-catalyzed intramolecular cyclization reaction of arylcyanopropionate: Geminal substitution effect on superelectrophilicity

Journal of Organic Chemistry

Volumn 73, Issue 11, 2008, Pages 4219-4224

  Nakamura, Satoshi ^a,b   Sugimoto, Hiromichi ^a   Ohwada, Tomohiko ^a  

^a UNIVERSITY OF TOKYO   (Japan)

^b UNIVERSITY OF EDINBURGH   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; AMINES; AROMATIC COMPOUNDS; ATOMIC PHYSICS; ATOMS; CARBON; CHEMICAL REACTIONS; COMPUTER NETWORKS; CYANIDES; DEUTERIUM; ESTERIFICATION; ESTERS; NITROGEN; ORGANIC COMPOUNDS; REACTION KINETICS;

(E ,3E) PROCESS; AMINO GROUPS; AROMATIC CARBONS; CHEMICAL EQUATIONS; CYCLIZATION REACTIONS; DEUTERIUM EXCHANGE; ESTER GROUPS; INTRAMOLECULAR CYCLIZATION; NITROGEN ATOMS; PROTONATED; REACTIVITY (CHEMICAL); RING CLOSING REACTIONS; SUBSTITUTION EFFECTS; SUPER ACIDS; SUPERELECTROPHILICITY;

CYCLIZATION;

ACETIC ACID; AMINO ACID; BETA AMINO ACID; CATION; DEUTERIUM; ESTER; NITRILE; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; PROPIONIC ACID;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CYCLIZATION; ELECTROPHILIC STRESS; PROTON TRANSPORT; QUANTUM YIELD; RING CLOSING METATHESIS; SUBSTITUTION REACTION;

ACIDS; CATALYSIS; CYCLIZATION; MAGNETIC RESONANCE SPECTROSCOPY; PROPIONATES; SPECTROMETRY, MASS, ELECTROSPRAY IONIZATION;

EID: 44949233806     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo800674h     Document Type: Article

References (35)

1. (a) Nakamura, S.; Uchiyama, M.; Ohwada, T. J. Am. Chem. Soc. 2003, 125, 5282-5283.
2. (b) Nakamura, S.; Sugimoto, H.; Ohwada, T. J. Am. Chem. Soc. 2007, 129, 1724-1732.
3. (a) Moustafa, A. H.; Hitzler, M. G.; Lutz, M.; Jochims, J. C. Tetrahedron 1997, 53, 625-640.
4. (b) Colquhoun, H. M.; Lewis, D. F.; Williams, D. J. Org. Lett. 2001, 3, 2337-2340.
5. (c) Udwary, D. W.; Casillas, L. K.; Townsend, C. A. J. Am. Chem. Soc. 2002, 124, 5294-5303.
6. (d) Henninger, J.; Polborn, K.; Mayr, H. J. Org. Chem. 2000, 65, 3569-3570.
7. (e) Urgaonkar, S.; Shaw, J. T. J. Org. Chem. 2007, 72, 4582-4585.
8. Conversion of a cyano group to an amine functional group occurs in a few synthetic reactions of heterocyclic compounds, such as the Gewald aminothiophen synthesis (Li, J. J. Name Reactions in Heterocyclic Chemistry: John Wiley & Sons: Hoboken, NJ, 2005; Chapter 5). The reactions involve aromatization of heterocycles, i.e., enamine formation due to the presence of acidic protons at the α-position of the cyano group.
9. (a) Olah, G. A.; Klumpp, D. A. Acc. Chem. Res. 2004, 37, 211-220.
10. (b) Olah, G. A. Angew. Chem., Int. Ed. Engl. 1993, 32, 767-788.
11. (c) Olah, G. A.; Klumpp, D. A. Superelectrophiles and Their Chemistry; John Wiley & Sons: Hoboken, NJ, 2008.
12. An extended reaction time (48 h) afforded a complex mixture of products.
13. Fustero, S.; Garcia de la Torre, M.; Jofré, V.; Carlón, R. P.; Navarro, A.; Fuentes, A. S.; Carrió, J. S. J. Org. Chem. 1998, 63, 8825-8836.
14. Miura, T.; Harumashi, T.; Murakami, M. Org. Lett. 2007, 9, 741-743.
15. The substrates for the cyclization reaction, methyl 3-aryl-2- cyanopropionates, were easily synthesized from the corresponding arylaldehyde and methyl cyanoacetate, via Knøvenagel condensation and subsequent reduction with hydrogenation or the triethylamine - formic acid azeotrope. See the Supporting Information.
16. 1H NMR spectra of the crude product and of the separated recovered substrate indicated that no proton or deuterium at the methylene position was exchanged under the reaction conditions.
17. (a) Hammett, L. P.; Deyrup, A. J. J. Am. Chem. Soc. 1932, 54, 2721-2739.
18. (b) Paul, M. A.; Long, F. A. Chem. Rev. 1957, 57, 1-45.
19. (c) Jorgenson, J. J.; Hartter, D. R. J. Am. Chem. Soc. 1963, 85, 878-883.
20. (d) Ryabova, R. S. Zh. Fiz. Khim. 1966, 40, 339-345.
21. (a) Saito, S.; Saito, S.; Ohwada, T.; Shudo, K. Chem. Pharm. Bull. 1991, 39, 2718-2720.
22. (b) Saito, S.; Sato, Y.; Ohwada, T.; Shudo, K. J. Am. Chem. Soc. 1994, 116, 2312-2317.
23. For recent representative studies on the acidity dependence of superacid-catalyzed organic reactions, see: (a) Olah, G. A.; Mathew, T.; Marinez, E. R.; Esteves, P. M.; Etzkorn, M.; Rasul, G.; Prakash, G. K. S. J. Am. Chem. Soc. 2001, 123, 11556-11561.
24. (b) Klumpp, D. A.; Baek, D. N.; Prakash, G. K. S.; Olah, G. A. J. Org. Chem. 1997, 62, 6666-6671.
25. (c) Yokoyama, A.; Ohwada, T.; Shudo, K. J. Org. Chem. 1999, 64, 611-617.
26. (d) Ohwada, T.; Suzuki, T.; Shudo, K. J. Am. Chem. Soc. 1998, 120, 4629-4637.
27. (e) Ohwada, T.; Yamazaki, T.; Suzuki, T.; Saito, S.; Shudo, K. J. Am. Chem. Soc. 1996, 118, 6220-6224.
28. (f) Sato, Y.; Yato, M.; Ohwada, T.; Saito, S.; Shudo, K. J. Am. Chem. Soc. 1995, 117, 3037-3043.
29. Arnet, E. M. Prog. Phys. Org. Chem. 1963, 1, 223-403.
30. 3 to TFA.
31. (a) Levy, G. C.; Cargioli, J. D.; Racela, W. J. Am. Chem. Soc. 1970, 92, 6238-6246.
32. (b) Olah, G. A.; Westerman, P. W. J. Org. Chem. 1973, 38, 1986-1992.
33. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A;.; Cheeseman, J. R.; Montogomery, J. A., Jr.; Kudin, K. N.; Burant, J. C.; Millam, J. M. Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Peterson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, G.; Dapprich, S.; Daniels, A. K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Gaussian, Inc.: Pittsburgh, PA, 2003.
34. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.
35. (b) Wolinski, K.; Hinton, J. F.; Pulay, P. J. Am. Chem. Soc. 1990, 112, 8251-8260.