ol8b00984_si_001.pdf (7.66 MB)
Straightforward Entry toward Highly Substituted 2,3-Dihydrobenz[b]oxepines by Ring Expansion of Benzopyryliums with Donor–Acceptor Diazo Compounds
journal contribution
posted on 2018-04-20, 17:20 authored by Thibaut Courant, Morgane Pasco, Thomas LecourtYlide-type
reactivity of diazo compounds is exploited in a new
way to prepare benzo[b]oxepines thanks to the formation
of three chemical bonds and two contiguous and highly substituted
stereocenters in a single pot. This cationic reaction cascade first
involves addition of a donor–acceptor-substituted diazo compound
to a benzopyrylium. Selective 1,2 migration of the endocyclic C–C
bond then results in a ring-expansion and generates a second oxocarbenium
that is trapped by a nucleophile added sequentially.