Stereoselective [4 + 3] annulation of azadienes and ethyl 4-bromo-3-oxobutanoate: construction of benzindeno-fused azepine derivatives

Abstract

The benzindenoazepine ring system is an attractive scaffold for biologically active compounds. This work reported a NaH-promoted cycloaddition between azadienes and ethyl 4-bromo-3-oxobutanoate, which delivered a series of benzindenoazepines with good yields and stereoselectivities. Such benzindenoazepine derivatives were not easily obtained by using a traditional approach. The application of this cycloaddition strategy has been extended to azadienes bearing a benzofuran or benzothiophene moiety. The utility of this method was showcased by gram-scale experiments and synthetic transformations of the product.