Engineering a Dual-Functionalized PolyHIPE Resin for Photobiocatalytic Flow Chemistry.

The use of a dual resin for photobiocatalysis, encompassing both a photocatalyst and an immobilized enzyme, brings several challenges, including effective immobilization, maintaining photocatalyst and enzyme activity and ensuring sufficient light penetration. However, the benefits, such as integrated processes, reusability, easier product separation, and potential for scalability, can outweigh these challenges, making dual resin systems promising for efficient and sustainable photobiocatalytic applications. In this study, we employed a photosensitizer-containing porous emulsion-templated polymer as a functional support that is used to covalently anchor a chloroperoxidase from Curvularia inaequalis (CiVCPO). We demonstrate the versatility of this heterogeneous photobiocatalytic material, which enables the bromination of four aromatic substrates, including rutin-a natural occurring flavonol-under blue light (456 nm) irradiation and continuous flow conditions.

The Photochemical Mediated Ring Contraction of 4H-1,2,6-Thiadiazines To Afford 1,2,5-Thiadiazol-3(2H)-one 1-Oxides.

1,2,6-Thiadiazines treated with visible light and 3O2 under ambient conditions are converted into difficult-to-access 1,2,5-thiadiazole 1-oxides (35 examples, yields of 39-100%). Experimental and theoretical studies reveal that 1,2,6-thiadiazines act as triplet photosensitizers that produce 1O2 and then undergo a chemoselective [3 + 2] cycloaddition to give an endoperoxide that ring contracts with selective carbon atom excision and complete atom economy. The reaction was optimized under both batch and continuous-flow conditions and is also efficient in green solvents.

8,8'-(Benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(quinolin-4(1H)-one): a twisted photosensitizer with AIE properties.

A new benzothiadiazole (BTZ) luminogen is prepared via the Suzuki-Miyaura Pd-catalysed C-C cross-coupling of 8-iodoquinolin-4(1H)-one and a BTZ bispinacol boronic ester. The rapid reaction (5 min) affords the air-, thermo-, and photostable product in 97% yield as a yellow precipitate that can be isolated by filtration. The luminogen exhibits aggregated-induced emission (AIE) properties, which are attributed to its photoactive BTZ core and nonplanar geometry. It also behaves as a molecular heterogeneous photosensitizer for the production of singlet oxygen under continuous flow conditions.

Mechanochemical Synthesis of N-Aryl Amides from O-Protected Hydroxamic Acids.

Two robust and efficient mechanochemical protocols for the synthesis of an array of N-arylamides have been developed. This was achieved by a C-N cross-coupling between O-pivaloyl hydroxamic acids and aryl iodides or aryl boronic acids, in the presence of a stoichiometric amount of a copper mediator. The effectiveness of this method is highlighted by the high-yielding (up to 94 %), scalable (up to 8 mmol), and rapid (20 minutes) synthesis of N-aryl amides (15 examples), using a variety of deactivated and sterically encumbered substrates, whilst employing mild conditions and in the absence of solvents. In addition, it was determined that whilst the O-pivaloyl hydroxamic acid precursors can be synthesised mechanochemically, iron contamination originating from the steel jars was found to occur which can hinder the efficacy of this process. Furthermore, 3D printing was used to produce custom milling jars that could successfully accommodate a scaled-up version of the two protocols.