Exploring the in situ Utilization of Cyclic Imine Intermediates Generated by Isocyanoacetate Cycloaddition: Convergent Assembly of cis-3a,8a-Hexahydropyrrolo[2,3-b]indole Scaffolds

Under copper(I) or silver(I)/base cocatalysis conditions, transient 2H‐pyrroline intermediates generated by the cycloaddition of isocyanoacetates and olefins can be in situ subjected to further transformations. A strategically novel, convergent, mild, efficient, general and atom‐economic access to cis‐3a,8a‐hexahydropyrrolo[2,3‐b]indoles, which are core scaffolds in many biologically important natural products, has been developed based on this concept.