Manganese-Catalyzed Regioselective Dehydrogenative C- versus N-Alkylation Enabled by a Solvent Switch: Experiment and Computation.

The first base metal-catalyzed regioselective dehydrogenative alkylation of indolines using readily available alcohols as the alkylating reagent is reported. A single air- and moisture-stable manganese catalyst provides access to either C- or N-alkylated indoles depending on the solvent used. Mechanistic studies indicate that the reaction takes place through a combined acceptorless dehydrogenation and hydrogen autotransfer strategy.