Ruthenium-catalyzed selective α-deuteration of aliphatic nitrites using D2O

被引:26
作者
Krishnakumar, Varadhan [1 ]
Gunanathan, Chidambaram [1 ]
机构
[1] HBNI, NISER, Sch Chem Sci, Bhubaneswar 752050, Khurda, India
关键词
METAL-LIGAND COOPERATION; HYDROGEN ISOTOPE-EXCHANGE; BOND ACTIVATION; H/D EXCHANGE; AROMATIZATION-DEAROMATIZATION; PINCER COMPLEXES; DRUG-METABOLISM; DEUTERIUM; NITRILES; ALCOHOLS;
D O I
10.1039/c8cc03971b
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Selective catalytic alpha-deuteration of aliphatic nitriles using deuterium oxide as a deuterium source is reported. A PNP-ruthenium pincer complex catalyzed the alpha-deuteration of aliphatic nitrites 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 alpha-position of the nitrile, is proposed as a plausible reaction mechanism.
引用
收藏
页码:8705 / 8708
页数:4
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