1. Manganese-Pincer-Catalyzed Nitrile Hydration, α-Deuteration, and α-Deuterated Amide Formation via Metal Ligand Cooperation
- Author
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Quan-Quan Zhou, Sayan Kar, David Milstein, Yehoshoa Ben-David, You-Quan Zou, and Yael Diskin-Posner
- Subjects
Letter ,Nitrile ,010405 organic chemistry ,Ligand ,chemistry.chemical_element ,General Chemistry ,Manganese ,010402 general chemistry ,01 natural sciences ,Toluene ,Medicinal chemistry ,Catalysis ,α-deuteration ,0104 chemical sciences ,Pincer movement ,Solvent ,chemistry.chemical_compound ,manganese pincer complex ,chemistry ,metal−ligand cooperation ,Amide ,nitriles ,hydration - Abstract
A simple and efficient system for the hydration and α-deuteration of nitriles to form amides, α-deuterated nitriles, and α-deuterated amides catalyzed by a single pincer complex of the earth-abundant manganese capable of metal-ligand cooperation is reported. The reaction is selective and tolerates a wide range of functional groups, giving the corresponding amides in moderate to good yields. Changing the solvent from tert-butanol to toluene and using D2O results in formation of α-deuterated nitriles in high selectivity. Moreover, α-deuterated amides can be obtained in one step directly from nitriles and D2O in THF. Preliminary mechanistic studies suggest the transformations contributing toward activation of the nitriles via a metal-ligand cooperative pathway, generating the manganese ketimido and enamido pincer complexes as the key intermediates for further transformations.
- Published
- 2021