Catalytic Method of Deuterium Gas Generation Using D_2O and Pd/C and Its Application to Synthesis of Deuterium-Labeled Compound

研究了Pd/ c催化的D_2O与H_2交换反应及其在氘标记化合物制备中的应用。密封在反应瓶中的H_2有效地转化为纯D_2，可用于多种还原性官能团的一锅还原氘化。此外，烯烃和乙炔的化学选择性脱氢是通过添加微量的Ph_2S来完成的，同时保留了各种其他可还原的官能团。提出了一种捕集生成的D_2气的方法。h_2 - d2交换反应的显著特点是高效、廉价、环保和方便。此外，在不需要昂贵的D_2气体的情况下，以非均相Pd/C为催化剂，在苯基上进行了简单、温和、区域选择性的H-D交换反应。本方法可获得相应的氘标记化合物，且氘效率优异。在少量氢气存在的情况下，使用10%的Pd/C，以较便宜的D-2O作为氘源，在室温下进行72 h的高效h - d交换，并且在温和加热（50℃）条件下，该反应显著加速，从而缩短了反应时间，扩大了底物的适用性。H-D交换反应也可用于苯醚的氘化，而苯醚在Pd/C催化的加氢条件下通常不稳定，使用Pd/C（en）代替Pd/C具有较高的氘效率。此外，使用the和D_2O（7:3）混合溶剂成功地抑制了相应苯醚的氢解反应。本方法对复杂的^1H核磁共振谱图的简化也非常有用。这些方法的普遍效用将使这些简单的技术成为广泛的氘化程序的一个有吸引力的补充。

The Pd/C-catalyzed H_2-D_2 exchange reaction between D_2O and H_2 and its application to the preparation of deuterium labeled compounds have been demonstrated. H_2 sealed in the reaction flask was efficiently converted into pure D_2, which can be used for the one-pot reductive deuteration of a variety of reducible functionalities. Furthermore, the chemoselective deuterogenation of olefins and acetylenes was accomplished by the addition of a trace amount of Ph_2S with retention of the various other reducible functionalities. A method of capturing the generated D_2 gas was also developed. The significant features of the H_2-D_2 exchange reaction are efficiency, inexpensiveness, environmental-friendly and convenience. Furthermore, a simple, mild, and regioselective H-D exchange reaction at the benzylic sites using the heterogeneous Pd/C as a catalyst without expensive D_2 gas was developed. The present method can afford the corresponding deuterium-labelled compounds with excellent deuterium efficiency. The use of 10% Pd/C in the presence of a small amount of hydrogen gas could achieve an efficient H-D exchange using the less expensive D-2O as the deuterium source at room temperature for 72 h. Furthermore, this reaction is dramatically accelerated under mild heating (50℃) conditions, resulting in shortening the reaction time and expanding the applicability of the substrates. The H-D exchange reaction could also be used for the deuteration of benzyl ethers, which were generally unstable under Pd/C-catalyzed hydrogenation conditions, with a high deuterium efficiency using Pd/C(en) instead of Pd/C. Furthermore, the use of THE and D_2O mixed (7:3) solvent successfully suppressed the hydrogenolysis of the corresponding benzyl ether. The present method would also be very useful for the simplification of complex ^1H NMR charts.The general utility of these methodologies will make such simple techniques an attractive addition to the wide range of deuteration procedures.