We recently developed a very direct strategy for the synthesis of cyclic guanidines employing 2-amido-1,3-diamino allylic cation intermediates, generated under oxidative conditions, which undergo a net 3+2 cycloaddition with alkenes. Toward expanding the scope of this process, we made more reactive variants of the allyl cation intermediate with a goal of expanding the repertoire of participating alkene substrates. In addition, we pursued optimization of an unusual by-product from dienes leading to tetra-functionalization of these substrates which we propose proceeds through a sequence involving amination, benzyloxylation, and intramolecular aziridination. Applications of this direct guanidinylation of alkenes will be described including efforts toward various members of the pyrrole-2-amino imidazole alkaloid family.

Net [3+2] cycloadditions toward cyclic guanidines: Mechanism and applications to natural product total synthesis

ACS Spring 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.