A novel synthetic method for angularly functionalized polycyclic systems by vinylogous wolff rearrangement of β, γ-unsaturated diazoketones

Palladium(0)-Catalyzed Benzylic C(<i>sp</i>³)–H Functionalization for the Concise Synthesis of Heterocycles and Its Applications

“…Although tetrahydro-2H-fluorenes are considered useful intermediates for the construction of complex systems, there were no general synthetic methods for preparation of these compounds in the literature when we initiated this work. 119,120) Considering our experience of C(sp )-H activation processes. 122,123) Enol triflate 70, which was prepared from cyclohexanone through sequential Pd-catalyzed α-arylation 124) and triflation reactions, was treated with Pd(PPh 3 ) 4 (10 mol%), Cs 2 CO 3 (1.1 equiv.…”

Copper(II) Trifluoromethanesulfonate

“…is indicative of a reactive and less discriminating intermediate compared to carbenoids generated from N 2 CHCO 2 Et with other Cu II reagents (eq 11) 10. Angularly functionalized polycyclic systems may be prepared from β,γ-unsaturated diazo ketones by a vinylogous Wolff rearrangement in the presence of copper(II) triflate.…”