Photocatalytic trifluoromethoxylation of arenes and heteroarenes in continuous-flow

Nyuchev, Alexander V.; Wan, Ting; Cendón, Borja; Sambiagio, Carlo; Struijs, Job J.C.; Ho, Michelle; Gulı́as, Moisés; Wang, Ying; Noël, Timothy

doi:10.3762/bjoc.16.111

Cited by 19 publications

(20 citation statements)

References 33 publications

(58 reference statements)

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“…Importantly, this photocatalytic trifluoromethoxylation process could be scaled up when performed in a flow system with a comparable yield to the batch reactions, but a much greater reaction efficiency was obtained. 242 As an important supplement to trifluoromethoxylations, direct difluoromethoxylations are also appealing, considering their application potential in medicinal chemistry. Recently, the Ngai group reported the photocatalytic C−H difluoromethoxy radical-mediated difluoromethoxylation of aromatic compounds 46-2 (Scheme 46).…”

Section: Generation Of Alkoxy Radicals From O−o Bondsmentioning

confidence: 99%

“…A straightforward mechanism has been proposed where the single-electron transfer between photoexcited *Ru(bpy) 3 2+ ( E 1/2 III/ * II = −0.81 V vs SCE) and the OCF 3 reagent can effectively release the trifluoromethoxy radical for the desired C–H trifluoromethoxylation. Importantly, this photocatalytic trifluoromethoxylation process could be scaled up when performed in a flow system with a comparable yield to the batch reactions, but a much greater reaction efficiency was obtained …”

Section: Generation Of Alkoxy Radicals From O–n Bondsmentioning

confidence: 99%

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Alkoxy Radicals See the Light: New Paradigms of Photochemical Synthesis

et al. 2021

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Alkoxy radicals are highly reactive species that have long been recognized as versatile intermediates in organic synthesis. However, their development has long been impeded due to a lack of convenient methods for their generation. Thanks to advances in photoredox catalysis, enabling facile access to alkoxy radicals from bench-stable precursors and free alcohols under mild conditions, research interest in this field has been renewed. This review comprehensively summarizes the recent progress in alkoxy radical-mediated transformations under visible light irradiation. Elementary steps for alkoxy radical generation from either radical precursors or free alcohols are central to reaction development; thus, each section is categorized and discussed accordingly. Throughout this review, we have focused on the different mechanisms of alkoxy radical generation as well as their impact on synthetic utilizations. Notably, the catalytic generation of alkoxy radicals from abundant alcohols is still in the early stage, providing intriguing opportunities to exploit alkoxy radicals for diverse synthetic paradigms.

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Section: Generation Of Alkoxy Radicals From O−o Bondsmentioning

confidence: 99%

Section: Generation Of Alkoxy Radicals From O–n Bondsmentioning

confidence: 99%

Alkoxy Radicals See the Light: New Paradigms of Photochemical Synthesis

et al. 2021

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“…253 AbbVie and Noel have recently reported a protocol for the C(sp 2 )−H trifluoromethoxylation of (hetero)arenes using Ngai's second-generation reagent (123) 254 under visible light irradiation in continuous flow (Scheme 96). 255 This new methodology builds on the seminal work by Ngai 254,256 and Togni 257 for the incorporation OCF 3 to (hetero)arenes. Mechanistically, the single electron reduction of a redox-active trifluoromethoxylating reagent is required to generate the OCF 3 radical via mesolytic cleavage of a N−OCF 3 bond.…”

Section: Introduction Of Fluorinated Functional Groupsmentioning

confidence: 99%

Photocatalysis in the Life Science Industry

et al. 2021

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In the pursuit of new pharmaceuticals and agrochemicals, chemists in the life science industry require access to mild and robust synthetic methodologies to systematically modify chemical structures, explore novel chemical space, and enable efficient synthesis. In this context, photocatalysis has emerged as a powerful technology for the synthesis of complex and often highly functionalized molecules. This Review aims to summarize the published contributions to the field from the life science industry, including research from industrial-academic partnerships. An overview of the synthetic methodologies developed and strategic applications in chemical synthesis, including peptide functionalization, isotope labeling, and both DNA-encoded and traditional library synthesis, is provided, along with a summary of the state-of-the-art in photoreactor technology and the effective upscaling of photocatalytic reactions.

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“…The high surface-to-volume ratio in continuous-flow reactors, on the other hand, allows the best possible homogeneous irradiation of the reaction solution. Combined with high-power LEDs, continuous-flow reactors can reduce the reaction time from days to minutes and narrow the by-product spectrum, 14,15 making photochemical reactions attractive synthesis options for academic and industrial laboratories. 9,[16][17][18][19][20] With light as a reaction parameter, wavelength and intensity of the irradiation influence the outcome of the reaction, yet in the literature this information is rarely provided.…”

Section: Introductionmentioning

confidence: 99%