Amino-Claisen Rearrangement. IV. Quaternary Amino-Claisen Rearrangement of N-Allyljulolidinium Derivatives

Abstract

The amino-Claisen rearrangements of 9-unsubstituted and 9-substituted N-allyljulolidinium halides were investigated. The former compounds can be regarded as aniline derivatives in which the two ortho sites are occupied. In the latter compounds, the two ortho positions and the para position are all blocked. N-Allyljulolidinium halides rearranged into 9-allyljulolidine. However, 9-substituted N-allyljulolidinium halides gave 8-allyl-9-substituted julolidines. This meta rearrangement constitutes the first reported example of meta amino-Claisen rearrangement. The reaction pathways can be rationalized in terms of a combination of [3, 3] and [1, 2] sigmatropic rearrangements.