One-pot H/D exchange and low-coordinated iron electrocatalyzed deuteration of nitriles in D2O to α,β-deuterio aryl ethylamines

• Published in: Nature communications 2022-10, Vol.13 (1), p.5951-12, Article 5951
• Main Authors: Li, Rui, Wu, Yongmeng, Wang, Changhong, He, Meng, Liu, Cuibo, Zhang, Bin
• Format: Article
• Language: English
• Subjects: 140/131; 140/146; 140/58; 147/135; 147/137; 147/143; 639/638/224/685; 639/638/549/933; 639/638/77/886; Adsorption; Aromatic compounds; Carbon; Cyanide; Deuteration; Deuterium; Humanities and Social Sciences; Hydrogen; Hydrogen-deuterium exchange; Hydrogenation; Intermediates; Iron; Laboratories; Melatonin; Metabolism; multidisciplinary; Nanoparticles; Nitriles; Ratios; Room temperature; Science; Science (multidisciplinary); Substrates; Synthesis
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-022-33779-8

Developing a step-economical approach for efficient synthesis of α , β -deuterio aryl ethylamines ( α , β -DAEAs) with high deuterium ratios using an easy-to-handle deuterated source under ambient conditions is highly desirable. Here we report a room-temperature one-pot two-step transformation of aryl acetonitriles to α , β -DAEAs with up to 92% isolated yield and 99% α , β -deuterium ratios using D 2 O as a deuterium source. The process involves a fast α -C − H/C − D exchange and tandem electroreductive deuteration of C ≡ N over an in situ formed low-coordinated Fe nanoparticle cathode. The moderate adsorptions of nitriles/imine intermediates and the promoted formation of active hydrogen (H*) on unsaturated Fe sites facilitate the electroreduction process. In situ Raman confirms co-adsorption of aryl rings and the C ≡ N group on the Fe surface. A proposed H*-addition pathway is confirmed by the detected hydrogen and carbon radicals. Wide substrate scope, parallel synthesis of multiple α , β -DAEAs, and successful preparation of α , β -deuterated Melatonin and Komavine highlight the potential. One-pot efficient synthesis of α , β -deuterio aryl ethylamines with high deuterium ratios using an easy-to-handle deuterated source under ambient conditions is desirable. Here the author report the electrosynthesis of α , β -deuterio aryl ethylamines from aryl acetonitriles using D 2 O.