One-pot H/D exchange and low-coordinated iron electrocatalyzed deuteration of nitriles in D<sub>2</sub>O to α,β-deuterio aryl ethylamines.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 36216818.
- Also identified by DOI 10.1038/s41467-022-33779-8 and PMC identifier 9550836.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
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<sub>2</sub>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.