Photocatalytic and Photoinduced Phosphonylation of Aryl Iodides: A Batch and Flow Study

Abstract

Herein we disclose our study toward the synthesis of aryl phosphonates using either photocatalytic conditions or a photoinduced process. First, a phosphonylation reaction catalyzed by a copper complex was developed in batch, but unfortunately, it was not efficient under continuous flow. Alternatively, a photoinduced phosphonylation reaction was developed in continuous flow with a moderate efficiency. Finally, to enhance the yields observed under the continuous flow conditions for the scale-up, a complementary approach using another commercially available photoreactor was suggested to tackle the modest productivity observed in continuous flow.

Electron donor–acceptor complex photoactivation for deaminative alkynylation, alkenylation and allenylation: a comprehensive study

“…As part of our lasting industrial/academic collaboration, 15 we have been interested in the valorization of aliphatic amines, a ubiquitous functional group, to increase molecular complexity and to explore the chemical space. In the course of our investigations to revisit the deaminative alkynylation, we discovered that upon irradiation at 525 nm a mixture of the Katritzky salt I and alkynyl sulfone II in the presence of DIPEA led to the formation of the product 1 in a decent 46% yield (Scheme 2A).…”

Durability of Photosensitizers in a Photo-oxidation Reaction in a Novel Oscillatory Baffled Photo Reactor

“…This has promoted process innovations of synthesizing chemicals and pharmaceutical intermediates from unimolecular or radical chain reactions [1][2][3][4][5][6][7] to dual catalytic, bi-and multi-molecular transformations. [8][9][10][11][12][13][14][15] Photosensitizer/ photocatalyst plays a critical role in this synthesis, so much so, that the advancement of heterogeneous photocatalysis (HPCat) has been described as one of the greatest challenges and opportunities within photochemistry. 16 One question that remains to be answered is how durable a photosensitizer/ photocatalyst can be, which is the focus of this article.…”

Site-selective and metal-free C–H phosphonation of arenes via photoactivation of thianthrenium salts

“… 2 However, in recent years the implementation of electrocatalytic 3 and visible light-mediated 4 methods as a milder strategy for the preparation of phosphonates have been applied with success. In this field, photo-, 5 metallaphotoredox 6 and electron-donor–acceptor (EDA) methods 7 ( Scheme 1A ) have been employed using different aryl radical precursors, such as aryl halides, aminated arenes, or aryl sulfonates through homolytic cleavage of C(sp 2 )–heteroatom bonds. 8 In addition, two examples of light induced direct C(sp 2 )–H phosphonation have been reported in the same year.…”