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.

中文翻译：

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钌催化使用D ₂ O †的脂肪族腈选择性α-氘代

报道了使用氧化氘作为氘源的脂族腈的选择性催化α-氘代。PNP-钌夹杂物催化包括乙腈在内的脂肪腈的α-氘代。在较低的催化剂负载量（0.2至0.5 mol％）和温和条件下，发生了有效的氘化。由腈官能团和去质子化的催化中间体形成[2 + 2]环加合物，然后亚胺-烯胺互变异构和烯胺中间体与氘化氢之间的H / D交换导致在腈α位的选择性氘化被提出为合理的反应机理。