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

Tian Luo; Zi Wang; Yinlin Chen; Hengzhao Li; Mengqi Peng; Floriana Tuna; Eric J L McInnes; Sarah J Day; Jie An; Martin Schröder; Sihai Yang

doi:10.1002/anie.202306267

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

Angew Chem Int Ed Engl. 2023 Nov 27;62(48):e202306267. doi: 10.1002/anie.202306267. Epub 2023 Oct 26.

Authors

Tian Luo¹, Zi Wang¹, Yinlin Chen¹, Hengzhao Li², Mengqi Peng², Floriana Tuna^{1

3}, Eric J L McInnes^{1

3}, Sarah J Day⁴, Jie An², Martin Schröder¹, Sihai Yang^{1

5}

Affiliations

¹ Department of Chemistry, University of Manchester, Manchester, M13 9PL, UK.
² Department of Nutrition and Health, China Agricultural University, Beijing, 100193, China.
³ Photon Science Institute, University of Manchester, Manchester, M13 9PL, UK.
⁴ Diamond Light Source, Harwell Science Campus, Oxfordshire, OX11 0DE, UK.
⁵ College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Beijing, 100871, China.

Abstract

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 CD₃ CN 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.

Keywords: Dehalogenative Deuteration; EPR; Metal-Organic Frameworks; Photocatalysis; SXPD.

Abstract

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