ol9b02807_si_001.pdf (8.28 MB)
Diene-Transmissive Diels–Alder Sequences with Benzynes
journal contribution
posted on 2019-09-03, 20:03 authored by Josemon George, Jas S. Ward, Michael S. SherburnDiene-transmissive Diels–Alder
(DTDA) sequences are extraordinarily
powerful processes for the generation of fused bicyclic systems. Nonetheless,
only stable dienophiles have previously been deployed. Herein we report
DTDA sequences with a variety of substituted [3]dendralenes in the
first study to deploy arynes as dienophiles. We demonstrate the one-flask
generation of complex, aromatic-ring-containing, multicyclic systems
of relevance to medicinal chemistry. These synthetic operations provide
numerous successful examples of the otherwise challenging and rarely
reported intermolecular Diels–Alder reaction of acyclic 1,3-butadienes
with arynes, which is made possible due to the exalted reactivity
of dendralenic dienes.