Journal of Organic Chemistry
American Chemical Society
Treatment of chlorotriaryl derivatives 3a and 3d or fluorotriaryl derivatives 3b and 3e with potassium diisopropylamide afforded alkyl-shifted phenazine derivatives 5a/5b, rather than the expected 9-membered triazaorthocyclophane 2a. The phenazine derivatives were isolated in 78–98% yield depending on the halogen and alkyl group present. In the absence of the halogen (chloro or fluoro), the apparent alkyl shift proceeds more slowly and cannot proceed via the intermediacy of the aryne intermediate. Mechanistic possibilities include intramolecular nucleophilic attack on an aryne intermediate leading to a zwitterionic intermediate and alkyl transfer via a 5-endo-tet process, or via a Smiles rearrangement.
Becker, Daniel; Panagopoulos, Andria M.; Steinman, Doug; Goncharenko, Alexandra; Geary, Kyle; Schleisman, Carlene; Spaargaren, Elizabeth; and Zeller, Matthias. Apparent Alkyl Transfer and Phenazine Formation via an Aryne Intermediate. Journal of Organic Chemistry, 78, 8: , 2013. Retrieved from Loyola eCommons, Chemistry: Faculty Publications and Other Works, http://dx.doi.org/10.1021/jo302795w
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© 2013 American Chemical Society
Author Posting © American Chemical Society, 2013. This is the author's version of the work. It is posted here by permission of American Chemical Society for personal use, not for redistribution. The definitive version was published in Journal of Organic Chemistry, Volume 78, Issue 8, March 25, 2013. http://dx.doi.org/10.1021/jo302795w