Photocatalytic Dehalogenative Deuteration of Halides over a Robust Metal-Organic Framework

Deuterium labelling of organic compounds is an important process in chemistry. We report the first example of photocatalytic dehalogenative deuteration of both arylhalides and alkylhalides (40 substrates) over a metal-organic framework, MFM-300(Cr), using CD3CN as the deuterium source at room temperature. MFM-300(Cr) catalyses high deuterium incorporation and shows excellent tolerance to various functional groups. Synchrotron X-ray powder diffraction reveals the activation of halogenated substrates via confined binding within MFM-300(Cr). In situ electron paramagnetic resonance spectroscopy confirms the formation of carbon-based radicals as intermediates and reveals the reaction pathway. This protocol removes the use of precious-metal catalysts from state-of-the-art processes based upon direct hydrogen isotope exchange and shows high photocatalytic stability, thus enabling multiple catalytic cycles. The metal-organic framework MFM-300(Cr) acts as a photocatalyst for the dehalogenative deuteration of both arylhalides and alkylhalides (40 substrates) with high deuterium incorporation. Synchrotron PXRD reveals the activation of halogenated substrates via confined binding within MFM-300(Cr). In situ EPR spectroscopy confirms the formation of carbon-based radicals as intermediates and reveals the reaction pathway.image

Automated summary

This study reports a method for photocatalytic dehalogenative deuteration using a metal-organic framework, MFM-300(Cr), as the catalyst. The catalyst shows high deuterium incorporation and excellent tolerance to various functional groups. Synchrotron X-ray powder diffraction and in situ electron paramagnetic resonance spectroscopy reveal the mechanism and reaction pathway.