Sequential Ag(I)/Pd(0) Relay Catalysis Toward (4+3) Oxadiazepine Cycloadducts

Herein, we report a sequential Ag(I)/Pd(0) relay catalysis strategy enabling (4 + 3) cycloadditions between in situ generated C , N ‐azomethine imines and 2‐methylidenetrimethylene carbonates. After opti mization of the reaction conditions, an array of isoquinoline‐fused oxadiazepines was obtained showing broad functional group tolerance. The method was further demonstrated on gram scale and through a streamlined three‐step/one‐pot procedure from readily available ortho ‐alkynylbenzaldehydes. This work demonstrates that orthogonal Ag(I)/Pd(0) relay catalysis provides a powerful and general platform for the rapid construction of complex heterocyclic scaffolds.