Atroposelective Synthesis of N-Arylindoles via Enantioselective N-H Bond Insertion.

We present here a rhodium-catalyzed asymmetric N-H insertion reaction, which is a concerted process revealed by DFT calculations, for the synthesis of novel axially chiral N-arylindoles by the reaction between indoles and diazonaphthoquinones. The reaction occurs at the N1 rather than C2/C3 positions of indoles, providing the chiral N-arylindoles in good yields and excellent enantiomeric ratios. Furthermore, this protocol is also amenable to the synthesis of chiral N-arylcarbazoles with excellent enantiocontrol.

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