1.
J Org Chem
; 79(3): 1344-55, 2014 Feb 07.
Article
in English
| MEDLINE
| ID: mdl-24433159
ABSTRACT
Arynes are shown to insert into some CâX double bonds, leading to benzannulated four-membered rings. The strain of these rings allow for a ready, spontaneous opening to afford o-quinomethide analogues. Subsequent nucleophilic addition re-aromatizes the intermediates to achieve ortho-difunctionalization of arynes. In this report, we describe the aryne insertion into the CâC double bonds of vinylogous amides and the CâN double bonds of carbodiimides. The correlation and comparison with aryne single bond insertion chemistry will be discussed. Computational studies for the ring-opening step, as well as the nature of the o-quinomethide intermediates, will also be discussed.