51. Scalable Photocatalytic Oxidation of Methionine under Continuous-Flow Conditions

Noémie Emmanuel, Carlos Mendoza, Marc Winter, Clemens R. Horn, Alessandra Vizza, Laurent Dreesen, Benoît Heinrichs, and Jean-Christophe M. Monbaliu, Organic Process Research & Development, (2017) DOI: 10.1021/acs.oprd.7b00212

Highly efficient and chemoselective singlet oxygen oxidation of unprotected methionine was performed in water using a continuous mesofluidic reactor. Sustainable process engineering and conditions were combined to maximize process efficiency and atom economy, with virtually no waste generation and safe operating conditions. Three water-soluble metal-free photosensitizers [Rose Bengal, Methylene Blue, and tetrakis(4-carboxyphenyl)porphyrin] were assessed. The best results were obtained with Rose Bengal (0.1 mol %) at room temperature under white light irradiation and a slight excess of oxygen. Process and reaction parameters were monitored in real-time with in-line NMR. Other classical organic substrates (a-terpinene and citronellol) were oxidized under similar conditions with excellent performances. In-line NMR analysis was carried out with a 43 MHz Spinsolve Carbon NMR spectrometer from Magritek® equipped with the flow-through module.