The efficient dehydrosulfurization of thioamides to nitriles was carried out using indium(III) triflate as a catalyst. Based on the results of the initial study, the optimal reaction conditions required 5 mol% of indium(III) triflate with toluene as the practical solvent. Various thioamides were successfully converted to nitriles in high yields.
Satchell, D.P.N. (1977) Metal-Ion-Promoted Reactions of Organo-Sulphur Compounds. Chemical Society Reviews, 6, 345-371. http://dx.doi.org/10.1039/CS9770600345
Suzuki, H., Tani, H. and Takeuchi, S. (1985) Desulfurization of Thioketones and Thioamides with Diphosphorus Tetraiodide. Bulletin of the Chemical Society of Japan, 58, 2421-2422. http://dx.doi.org/10.1246/bcsj.58.2421
Kondo, K., Komamura, C., Murakami, M. and Takemoto, K. (1985) 2,4-Dichloro-5-nitropyrimidine as a New Dehydrating or Desulfhydrating Reagent. Synthetic Communications, 15, 171-177. http://dx.doi.org/10.1080/00397918508063784
Bose, D.S. and Goud, P.R. (1999) Aryl Chlorothionoformate: A New Versatile Reagent for the Preparation of Nitriles and Isonitriles under Mild Conditions. Tetrahedron Letters, 40, 747-748. http://dx.doi.org/10.1016/S0040-4039(98)02361-2
Sato, R., Itoh, K., Itoh, K., Nishina, H., Goto, T. and Saito, M. (1984) Novel Conversion of Aromatic Thioamides and Aldehydes into Nitriles with Elemental Sulfur and Sodium Nitrite in Liquid Ammonia. Chemistry Letters, 11, 1913-1916. http://dx.doi.org/10.1246/cl.1984.1913
Funakoshi, Y., Takido, T. and Itabashi, K. (1985) Facile Conversion of Primary Thioamides into Nitriles with Benzyl Chloride under Phase Transfer Conditions. Synthetic Communications, 15, 1299-1303. http://dx.doi.org/10.1080/00397918508077278
Avalos, M., Babiano, R., Duran, C.J., Jimenez, J.L. and Palacios, J.C. (1994) Reaction of Thioamides with Silver Carboxylates in Aprotic Media. A Nucleophilic Approach to the Synthesis of Imides, Amides, and Nitriles. Tetrahedron Letters, 35, 477-480. http://dx.doi.org/10.1016/0040-4039(94)85085-2
Avalos, M., Babiano, R., Cintas, P., Duran, C.J., Higes, F.J., Jimenez, J.L., Lopez, I. and Palacios, J.C. (1997) Reaction of Thioamides with Metal Carboxylates in Organic Media. Tetrahedron, 53, 14463-14480. http://dx.doi.org/10.1016/S0040-4020(97)00938-1
Yamaguchi, K., Yajima, K. and Mizuno, N. (2012) Facile Synthesis of Nitriles via Manganese Oxide Promoted Oxidative Dehy-drosulfurization of Primary Thioamides. Chemical Communications, 48, 11247-11249. http://dx.doi.org/10.1039/c2cc36635e
Lim, M.-I., Ren, W.-Y. and Klein, R.S. (1982) Facile Conversion of Primary Thioamides into Nitriles with Butyltin Oxides. Journal of Organic Chemistry, 47, 4594-4595. http://dx.doi.org/10.1021/jo00144a043
Hu, N.X., Aso, Y., Otsubo, T. and Ogura, F. (1985) Mild and Selective Oxidations with Polystyrene-Bound Diaryl Selenoxide. Chemistry Letters, 14, 603-606. http://dx.doi.org/10.1246/cl.1985.603
Hu, N.X., Aso, Y., Otsubo, T. and Ogura, F. (1986) Polymer-Supported Diaryl Selenoxide and Telluroxide as Mild and Selective Oxidizing Agents. Bulletin of the Chemical Society of Japan, 59, 879-884. http://dx.doi.org/10.1246/bcsj.59.879
Hu, N.X., Aso, Y., Otsubo, T. and Ogura, F. (1986) Novel Oxidizing Properties of p-Methoxybenzenetellurinic Acid Anhydride. Tetrahedron Letters, 27, 6099-6102. http://dx.doi.org/10.1016/S0040-4039(00)85408-8
Fukumoto, T., Matsuki, T., Hu, N.X., Aso, Y., Otsubo, T. and Ogura, F. (1990) Benzenetellurinic Mixed Anhydrides as Mild Oxidizing Agents. Chemistry Letters, 19, 2269-2272. http://dx.doi.org/10.1246/cl.1990.2269
Aso, Y., Omote, K., Takagi, S., Otsubo, T. and Ogura, F. (1995) Mild and Efficient Dehydrosulfurization of Thioamides to Nitriles Induced by Tellurium or Selenium Tetrachloride with Triethylamine. Journal of Chemical Research, Synopses, No. 4, 152-153.
Enthaler, S. (2011) Straightforward Iron-Catalyzed Synthesis of Nitriles by Dehydration of Primary Amides. European Journal of Organic Chemistry, 2011, 4760-4763. http://dx.doi.org/10.1002/ejoc.201100754
Enthaler, S. and Inoue, S. (2012) An Efficient Zinc-Catalyzed Dehydration of Primary Amides to Nitriles. Chemistry—An Asian Journal, 7, 169-175. http://dx.doi.org/10.1002/asia.201100493
Mineno, T. (2002) A Fast and Practical Approach to Tetrahydro-pyranylation and Depyranylation of Alcohols Using Indium Triflate. Tetrahedron Letters, 43, 7975-7978. http://dx.doi.org/10.1016/S0040-4039(02)01864-6
Mineno, T. and Kansui, H. (2006) High Yielding Methyl Esterification Catalyzed by Indium(III) Chloride. Chemical & Pharmaceutical Bulletin, 54, 918-919. http://dx.doi.org/10.1248/cpb.54.918
Mineno, T., Nikaido, N. and Kansui, H. (2009) One-Step Transformation of Tetrahydropyranyl Ethers Using Indium(III) Triflate as the Catalyst. Chemical & Pharmaceutical Bulletin, 57, 1167-1170. http://dx.doi.org/10.1248/cpb.57.1167
Mineno, T., Sakai, M., Ubukata, A., Nakahara, K., Yoshimitsu, H. and Kansui, H. (2013) The Effect of Indium(III) Triflate in Oxone-Mediated Oxidative Methyl Esterification of Aldehydes. Chemical & Pharmaceutical Bulletin, 61, 870-872. http://dx.doi.org/10.1248/cpb.c13-00072
Mineno, T., Tsukagoshi, R., Iijima, T., Watanabe, K., Miyashita, H. and Yoshimitsu, H. (2014) Reductive Coupling Reaction of Aldehydes Using Indium(III) Triflate as the Catalyst. Tetrahedron Letters, 55, 3765-3767. http://dx.doi.org/10.1016/j.tetlet.2014.05.079
Mineno, T., Yoshino, S. and Ubukata, A. (2014) Oxone-Mediated Oxidative Esterification of Heterocyclic Aldehydes Using Indium(III) Triflate. Green and Sustainable Chemistry, 4, 20-23. http://dx.doi.org/10.4236/gsc.2014.41004
Mineno, T., Shinada, M., Watanabe, K., Yoshimitsu, H., Miyashita, H. and Kansui, H. (2014) Highly-Efficient Conversion of Primary Amides to Nitriles Using Indium(III) Triflate as the Catalyst. International Journal of Organic Chemistry, 4, 1-6. http://dx.doi.org/10.4236/ijoc.2014.41001
Littke, A., Soumeillant, M., Kaltenbach III, R.F., Cherney, R.J., Tarby, C.M. and Kiau, S. (2007) Mild and General Methods for the Palladium-Catalyzed Cyanation of Aryl and Heteroaryl Chlorides. Organic Letters, 9, 1711-1714. http://dx.doi.org/10.1021/ol070372d
Grossman, O. and Gelman, D. (2006) Novel Trans-Spanned Palladium Complexes as Efficient Catalysts in Mild and Amine-Free Cyanation of Aryl Bromides under Air. Organic Letters, 8, 1189-1191. http://dx.doi.org/10.1021/ol0601038
Yang, C. and Williams, J.M. (2004) Palladium-Catalyzed Cyanation of Aryl Bromides Promoted by Low-Level Organotin Compounds. Organic Letters, 6, 2837-2840. http://dx.doi.org/10.1021/ol049621d
Katritzky, A.R., Akue-Gedu, R. and Vakulenko, A.V. (2007) C-Cyanation with 1-cyanobenzotriazole. ARKIVOC, 2007, 5-12. http://dx.doi.org/10.3998/ark.5550190.0008.302