- Ruthenium-catalyzed selective α-deuteration of aliphatic nitriles using D2O
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Selective catalytic α-deuteration of aliphatic nitriles using deuterium oxide as a deuterium source is reported. A PNP-ruthenium pincer complex catalyzed the α-deuteration of aliphatic nitriles including acetonitrile. Efficient deuteration occurred with a low catalyst load (0.2 to 0.5 mol%) and under mild conditions. A [2+2] cycloadduct formation from nitrile functionality and a deprotonated catalytic intermediate, followed by an imine-enamine tautomerization and a H/D exchange between the enamine intermediate and deuterium oxide leading to the selective deuteration at the α-position of the nitrile, is proposed as a plausible reaction mechanism.
- Krishnakumar, Varadhan,Gunanathan, Chidambaram
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- Alpha, beta-deuterated amine compound, deuterated drug and preparation method thereof
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The invention relates to an alpha, beta-deuterated amine compound, a deuterated drug and a reduction deuteration method of a nitrile organic matter for synthesizing the alpha, beta-deuterated amine compound. The method is characterized by comprising the f
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Paragraph 0010
(2021/03/03)
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- Manganese-Pincer-Catalyzed Nitrile Hydration, α-Deuteration, and α-Deuterated Amide Formation via Metal Ligand Cooperation
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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.
- Ben-David, Yehoshoa,Diskin-Posner, Yael,Kar, Sayan,Milstein, David,Zhou, Quan-Quan,Zou, You-Quan
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p. 10239 - 10245
(2021/08/24)
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