Silver(I)-Catalyzed Tandem Reaction of Enynones and 4-Alkenyl Isoxazoles: Synthesis of 2-(Furan-2-yl)-1,2-dihydropyridines.

Abstract

Silver(I)-catalyzed tandem reaction of enynones with 4-alkenyl isoxazoles provides access to 2-(furan-2-yl)-1,2-dihydropyridines. No competitive cyclopropanation of alkenes and O-H insertion via (2-furyl)carbene complexes were observed. The cascade reaction proceeds via the formation of (2-furyl)metal carbene intermediate, the N-O bond cleavage of 4-alkenyl isoxazoles/rearrangement, subsequent 6π electrocyclic reaction, and [1,5] H-shift. The successive construction of both 1,2-dihydropyridine skeleton and furan frame has been achieved in the one-pot reaction. A broad range of readily available enynones and 4-alkenyl isoxazoles are suitable to this protocol; however, when R3 is the alkyl group such as n-Bu and Me, a complicated mixture was generated without the desired products. In addition, in the case of R4 = bulky group such as R3'SiOCH2, the reaction gave an in situ oxo-product of (2-furyl)silver carbene. An atom-economic strategy for the synthesis of 2-(furan-2-yl)-1,2-dihydropyridines has been established.