Tania Mutchie Seminar Abstract

The Ritter Reaction is a chemical reaction that yields N-alkyl amides from the nucleophilic addition of a nitrile to a carbocation source in the presence of concentrated sulfuric acid. Although it is a simple method for forming sterically hindered amides, and a convenient precursor for N-t-alkyl amines, the high temperatures and stoichiometric amounts of acid often needed limit the scope of the reaction. Notable progress has been made to expand the applicability of the classic Ritter Reaction, including methods to stabilize carbocation intermediates, use of catalytic amounts of acid, and Ritter-type amination following C-H bond activation. Recently, iodine-mediated routes have been employed as environmentally-friendly methods to convert unactivated, tertiary C-H bonds into C-N bonds.

References

1. Benson, F. R.; Ritter, J. J., A new reaction of nitriles. III. Amides from dinitriles. Journal of the American Chemical Society 1949, 71 (12), 4128-4129.

2. Kiyokawa, K.; Takemoto, K.; Minakata, S., Ritter-type amination of C–H bonds at tertiary carbon centers using iodic acid as an oxidant. Chemical Communications 2016, 52 (89), 13082-13085.

3. Kiyokawa, K.; Watanabe, T.; Fra, L.; Kojima, T.; Minakata, S., Hypervalent Iodine (III)-Mediated Decarboxylative Ritter-Type Amination Leading to the Production of α-Tertiary Amine Derivatives. 2017.

4. Martinez, A. G.; Alvarez, R. M.; Vilar, E. T.; Fraile, A. G.; Hanack, M.; Subramanian, L., An improved modification of Ritter reaction. Tetrahedron Letters 1989, 30 (5), 581-582.

5. Ritter, J. J.; Minieri, P. P., A New Reaction of Nitriles. I. Amides from Alkenes and Mononitriles1. Journal of the American Chemical Society 1948, 70 (12), 4045-4048.

6. Sakaguchi, S.; Hirabayashi, T.; Ishii, Y., First Ritter-type reaction of alkylbenzenes using N-hydroxyphthalimide as a key catalyst. Chemical Communications 2002, (5), 516-517.

7. Sanz, R.; Martínez, A.; Guilarte, V.; Álvarez‐Gutiérrez, J. M.; Rodríguez, F., The Ritter reaction under truly catalytic Brønsted acid conditions. European Journal of Organic Chemistry 2007, 2007 (28), 4642-4645.

8. Sasaki, T.; Eguchi, S.; Toru, T.; Ito, K., Synthesis of Adamantane Derivatives. IX. The Ritter Reaction of 1-Hydroxymethyladamantane with Acetonitrile. Bulletin of the Chemical Society of Japan 1970, 43 (6), 1820-1824.