RESUMEN
A base-promoted olefin skeletal rearrangement strategy from para-quinone methides (p-QMs) and N-fluoroarenesulfonamides is reported, enabling direct nitrogen insertion of olefins to produce a series of multiarylated (Z)-N-sulfonyl amidines with complete stereoselectivity and generally good yields. Using p-QMs without o-hydroxy substituents gave triarylated N-sulfonyl amidines, whereas tetraarylated N,N'-disulfonyl amidines were synthesized with the existence of o-hydroxy groups.
RESUMEN
A new Lewis acid-catalyzed [2 + 2] cycloaddition/retroelectrocyclization (CA-RE)/1,6-addition relay of aurone-derived 1-azadienes and 1-alkynylnaphthalen-2-ols has been reported, leading to the regio- and diastereoselective synthesis of 1,2-dihydrobenzofuro[3,2-b]pyridine with a chiral carbon center and an axial chirality in good yields. This protocol enables the C-C double-bond scission/recombination to rapidly construct aza-heterocyclic architectures and features 100% atom utilization, a wide substrate scope, good compatibility with substituents, and excellent diastereoselectivity.
RESUMEN
Two classes of new catalytic spiroannulation-fluormethylfunctionaliztions of para-quinone methide (p-QM)-containing 1,5-enynes have been established under redox-neutral conditions. Palladium-catalyzed spiroannulation-iododifluoromethylation with ethyl difluoroiodoacetate oriented completely stereoselective access to (Z)-spiroindenes and the latter included copper-catalyzed three-component spiroannulation-cyanotrifluoromethylation starting from Togni's reagent and trimethylsilanecarbonitrile (TMSCN). Both reaction pathways involve fluoroalkyl radical-triggered 1,6-addition/5-exo-dig annulation/metal radical cross-coupling/reductive elimination sequence, providing practical and stereoselective protocols for rapidly constructing cyclohexadienone-containing spiroindenes with generally good yields.
