Acceptorless dehydrogenative synthesis of primary amides from alcohols and ammonia

Jie Luo, Quan Quan Zhou, Michael Montag, Yehoshoa Ben-David, David Milstein

Research output: Contribution to journalArticlepeer-review

12 Scopus citations

Abstract

The highly desirable synthesis of the widely-used primary amides directly from alcohols and ammonia via acceptorless dehydrogenative coupling represents a clean, atom-economical, sustainable process. Nevertheless, such a reaction has not been previously reported, and the existing catalytic systems instead generate other N-containing products, e.g., amines, imines and nitriles. Herein, we demonstrate an efficient and selective ruthenium-catalyzed synthesis of primary amides from alcohols and ammonia gas, accompanied by H2 liberation. Various aliphatic and aromatic primary amides were synthesized in high yields, with no observable N-containing byproducts. The selectivity of this system toward primary amide formation is rationalized through density functional theory (DFT) calculations, which show that dehydrogenation of the hemiaminal intermediate into primary amide is energetically favored over its dehydration into imine.

Original languageEnglish
Pages (from-to)3894-3901
Number of pages8
JournalChemical Science
Volume13
Issue number13
DOIs
StatePublished - 2 Mar 2022
Externally publishedYes

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