Ruthenium-catalyzed selective α-deuteration of aliphatic nitriles using D2O?

Chemical Communications Pub Date: 2018-07-19 DOI: 10.1039/C8CC03971B

Abstract

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.

Graphical abstract: Ruthenium-catalyzed selective α-deuteration of aliphatic nitriles using D2O
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