A Tandem Madelung Indole Synthesis Mediated by a LiN(SiMe3)2/CsF System

A tandem Madelung indole synthesis by the reaction of methyl benzoate and N-methyl-o-toluidine has been discovered. The combination of LiN(SiMe3)2 with CsF is the key factor, which secures the high efficiency of such tandem transformations. Simply combining methyl benzoate, N-methyl-o-toluidine LiN(SiMe3)2, and CsF generated a diverse array of N-methyl-2-phenylindoles (31 examples, 50-90% yields). Furthermore, the scalability and the poststructural modifications of this indole synthesis were demonstrated.