A new facet of amide synthesis by tandem acceptorless dehydrogenation of amines and oxygen transfer of DMSO

We have developed a new catalytic system for preparing amides by tandem acceptorless dehydrogena-tion of amines and oxygen transfer of DMSO. This system shows very good catalytic activity and selectiv-ity, a variety of primary amines and even diamines are converted into the corresponding amides in good to quantitative yields (>99 %). The unprecedented catalytic performance of this binuclear ruthenium com-plex was attributed to a unique chelating model wherein one Ru center combines with N atom of RCH@NH produced from the dehydrogenation of RCH2NH2 and the other co-ordinates with the S atom of DMSO, thus bringing the DMSO and imine molecules into proximate to enhance the efficiency of the oxygen transfer from DMSO via a six-membered ring transition state. The mechanism study indicated that the oxygen in the product amides came from DMSO and C-H bond cleavage in DMSO was the rate determining step. CO 2022 Elsevier Inc. All rights reserved.

Automated summary

We have developed a new catalytic system for preparing amides using tandem acceptorless dehydrogenation of amines and oxygen transfer of DMSO. This system demonstrates excellent catalytic activity and selectivity, converting various primary amines and even diamines into the corresponding amides with yields ranging from good to quantitative (>99%). The remarkable catalytic performance of this binuclear ruthenium complex is attributed to a unique chelating model that allows efficient oxygen transfer from DMSO via a six-membered ring transition state.