Chemo- and Diastereoselective Acylfluorination of Nonactivated Olefins to Access Benzo[b]azepines
Xingfeng Liu1, Yuxi Wang1, Tao Xu1,2
1Molecular Synthesis Center and Key Laboratory of Marine Drugs, Ministry of Education, School of Medicine and Pharmacy, Ocean University of China, 5 Yushan Road, Qingdao, Shandong 266003, China.
Abstract:
Here, we describe a transition-metal-free condition that realized the intramolecular acylfluorination of unactivated olefins. It was designed to access seven-membered-ring-containing benzo[b]annulenones from readily prepared 2-allylamino benzoic acids. The formation of a broad scope of electronically and sterically varied benzo[b]annulenones was demonstrated (>30 examples, up to 88% yield and >20:1 dr ratio). Mechanistic studies indicated that the in situ formed XatlFluor-E-activated anhydride was the active species and induced an electrophilic 7-endo-trig cyclization, followed by fluoride capture of the cation.
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