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Atom-Economical and Tandem Conversion of Nitriles to N‑Methylated Amides Using Methanol and Water

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journal contribution
posted on 21.10.2019, 18:05 by Bhaskar Paul, Milan Maji, Sabuj Kundu
A cobalt complex catalyzed tandem conversion of nitrile to N-methylated amide is described using a methanol and water mixture. Using this protocol, several nitriles were directly and efficiently converted to the desired N-methylated amides. Kinetic experiments using H2O18 and CD3OD suggested that water and methanol were the source of the oxygen atom and methyl group, respectively, in the final N-methylated amides. Importantly, the participation of active Co­(I)–H species in this transformation was realized from the control experiment. The kinetic isotope effect (KIE) study suggested that the activation of the C–H bond of methanol was a kinetically important step. The Hammett plot confirmed that the reaction was faster with the electron deficient nitriles. In addition, the plausible pathway for the formation of N-methylated amides from the nitriles was supported by the computational study.