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

Article abstract of DOI:10.1021/acscatal.9b03916

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.

Full text of DOI:10.1021/acscatal.9b03916

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Letter
Atom-Economical and Tandem Conversion of Nitriles
to N-Methylated Amides using Methanol and Water
Bhaskar Paul, Milan Maji, and Sabuj Kundu
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.9b03916 • Publication Date (Web): 11 Oct 2019
Downloaded from pubs.acs.org on October 12, 2019
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