Synthesis of Benzo[1,4]heterocycles using Palladium Catalyzed Heck Reaction to Vinylogous Carbonates/Carbamates: Unexpected Formation of Indoles via Carbopalladation Intercepted by Nucleopalladation.

An efficient protocol for the stereoselective synthesis of benzo[1,4]heterocycles via palladium catalyzed Heck reaction on o-halo-aryl-oxa/thia/aza tethered vinylogous carbonates/carbamates/esters has been developed. Unexpected formation of indoles is observed when unprotected 2-iodoaniline tethered vinylogous carbonates are subjected to the Heck reaction. Mechanistic studies indicate that formation of these indoles is an outcome of the interception of the carbopalladation step by nucleopalladation. The method can be used to gain rapid access to the core skeleton of abacopterin A-C.