Ag-Catalyzed Asymmetric Interrupted Barton-Zard Reaction Enabling the Enantioselective Dearomatization of 2- and 3-Nitroindoles.

We disclose a Ag-catalyzed asymmetric interrupted Barton-Zard reaction of α-aryl-substituted isocyanoacetates with 2- and 3-nitroindoles, which enables the dearomatization of nitroindoles and hence offers rapid access to an array of optically active tetrahydropyrrolo[3,4- b ]indole derivatives bearing three contiguous stereogenic centers, including two tetrasubstituted chiral carbon atoms with pretty outcomes (up to 99% yield, 91:9 dr, and 96% ee). The synthetic potential of the protocol was showcased by the gram-scale reaction and versatile transformations of the product.