Computational insights into the mechanisms and origins of switchable selectivity in gold(i)-catalyzed annulation of ynamides with isoxazoles via 6π-electrocyclizations of azaheptatrienyl cations.

ABSTRACT: Electrocyclizations of acyclic conjugated π-motifs have emerged as a versatile and effective strategy for accessing various ring systems with excellent functional group tolerability and controllable selectivity. Typically, the realization of 6π-electrocyclization of heptatrienyl cations to afford seven-membered motif has proven difficult due to the high-energy state of the cyclizing seven-membered intermediate. Instead, it undergoes the Nazarov cyclization, affording a five-membered pyrrole product. However, the incorporation of a Au(i)-catalyst, a nitrogen atom and tosylamide group in the heptatrienyl cations unexpectedly circumvented the aforementioned high energy state to afford a seven-membered azepine product via 6π-electrocyclization in the annulation of 3-en-1-ynamides with i

SUBMITTER: Badeji AA 

PROVIDER: S-EPMC10265590 | biostudies-literature | 2023 Jun

REPOSITORIES: biostudies-literature