Substrate-controlled divergent synthesis with ortho-vinyl-functionalised 1,3-enynes and imines via palladium catalysis

Presented herein is a substrate-controlled diversity-oriented approach to access skeletally different frameworks from ortho-vinyl-functionalised 1,3-enynes and imines via palladium catalysis. A variety of benzofulvenes were constructed in moderate to high yields, enantioselectivity and E-selectivity, through a cascade vinylogous addition, 5-exo-trig migratory insertion and & beta;-H elimination process. In addition, modifing the vinyl substitutions of 1,3-enyne substrates could switch the Oppolzer cyclisation into a 6-endo-trig pattern, which finally furnished formal 1-naphthylated amines enantioselectively under similar conditions. Moreover, the 2-furyl imine-derived naphthalene products further underwent a domino intramolecular Diels-Alder cycloaddition reaction, furnishing complex oxabicyclo[2.2.1]heptane architectures. The efficient construction of distinctly structured libraries exhibited well the versatility of the current substrate-controlled strategy.

Automated summary

A substrate-controlled diversity-oriented approach using palladium catalysis was developed to access skeletally different frameworks. Various benzofulvenes were constructed in good yields, enantioselectivity, and E-selectivity via a cascade reaction. By modifying the vinyl substitutions of the substrate, formal 1-naphthylated amines were selectively obtained. Furthermore, the naphthalene products underwent a Diels-Alder cycloaddition reaction, leading to complex oxabicyclo[2.2.1]heptane architectures. This substrate-controlled strategy demonstrated great versatility in constructing structurally diverse compounds.