On anionic Snieckus-Fries rearrangement of N,N-Di-tert-butoxycarbonyl-pyridin-4-amines

ORGN 738

Yahua Liu, yliu2@gnf.org, Qiang Ding, and Xu Wu. Genomics Institute of the Novartis Research Foundation, 10675 John Jay Hopkins Dr, San Diego, CA 92121
We further investigated the rearrangement of N,N-di-tert-butoxycarbonyl-pyridin-4-amines to tert-butyl 4-(tert-butoxycarbonylamine)-nicotinates which we have previously reported. Cross-over reaction supported a postulation of intramolecular migration of tert-butoxycarbonyl carbon. A mechanism was proposed to explain why the “in-between” product was formed as main product against steric hindrance. Other mechanistic aspects of the reaction were also studied. The rearrangement we studied provided a new addition to the examples of so called “anionic Snieckus-Fries rearrangement” which was mainly explored and expanded by Professor Victor Snieckus.