Manganese-Pincer-Catalyzed Nitrile Hydration, α-Deuteration, and α-Deuterated Amide Formation via Metal Ligand Cooperation.

Content Provider	Europe PMC
Author	Zhou, Quan-Quan Zou, You-Quan Kar, Sayan Diskin-Posner, Yael Ben-David, Yehoshoa Milstein, David
Copyright Year	2021
Abstract	A simple and efficientsystem for the hydration and α-deuterationof nitriles to form amides, α-deuterated nitriles, and α-deuteratedamides catalyzed by a single pincer complex of the earth-abundantmanganese capable of metal–ligand cooperation is reported.The reaction is selective and tolerates a wide range of functionalgroups, giving the corresponding amides in moderate to good yields.Changing the solvent from tert-butanol to tolueneand using D2O results in formation of α-deuteratednitriles in high selectivity. Moreover, α-deuterated amidescan be obtained in one step directly from nitriles and D2O in THF. Preliminary mechanistic studies suggest the transformationscontributing toward activation of the nitriles via a metal–ligandcooperative pathway, generating the manganese ketimido and enamidopincer complexes as the key intermediates for further transformations.
Related Links	https://europepmc.org/backend/ptpmcrender.fcgi?accid=PMC8383274&blobtype=pdf
Journal	ACS Catalysis [ACS Catal]
Volume Number	11
DOI	10.1021/acscatal.1c01748
PubMed Central reference number	PMC8383274
Issue Number	16
PubMed reference number	34476112
e-ISSN	21555435
Language	English
Publisher	AmericanChemical Society
Publisher Date	2021-08-03
Access Restriction	Open
Rights License	Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). © 2021 TheAuthors. Published by AmericanChemical Society
Subject Keyword	hydration α-deuteration manganese pincercomplex metal−ligand cooperation nitriles
Content Type	Text
Resource Type	Article
Subject	Chemistry Catalysis