Yao Ouyang

Biocatalysis has revolutionized chemical synthesis, providing sustainable methods for preparing various organic molecules. In enzyme-mediated organic synthesis, most reactions involve molecules operating from their ground states. Over the past 25 years, there has been an increased interest in enzymatic processes that utilize electronically excited states accessed through photoexcitation. These photobiocatalytic processes involve a diverse array of reaction mechanisms that are complementary to one another. This comprehensive review will describe the state-of-the-art strategies in photobiocatalysis for organic synthesis until December 2022. Apart from reviewing the relevant literature, a central goal of this review is to delineate the mechanistic differences between the general strategies employed in the field. We will organize this review based on the relationship between the photochemical step and the enzymatic transformations. The review will include mechanistic studies, substrate scopes, and protein optimization strategies. By clearly defining mechanistically-distinct strategies in photobiocatalytic chemistry, we hope to illuminate future synthetic opportunities in the area.

Abstract A large number of reagents have been developed for the synthesis of trifluoromethylated compounds. However, an ongoing challenge in trifluoromethylation reaction is the use of less expensive and practical trifluoromethyl sources. We report herein the unprecedented direct trifluoromethylation of (hetero)arenes using trifluoromethanesulfonic anhydride as a radical trifluoromethylation reagent by merging photoredox catalysis and pyridine activation. Furthermore, introduction of both the CF 3 and OTf groups of the trifluoromethanesulfonic anhydride into internal alkynes to access tetrasubstituted trifluoromethylated alkenes was achieved. Since trifluoromethanesulfonic anhydride is a low‐cost and abundant chemical, this method provides a cost‐efficient and practical route to trifluoromethylated compounds.

a-Tertiary amino acids are essential components of drugs and agrochemicals, yet traditional syntheses are step-intensive and provide access to a limited range of structures with varying levels of enantioselectivity. Here, we report the α-alkylation of unprotected alanine and glycine by pyridinium salts using pyridoxal (PLP)-dependent threonine aldolases with a Rose Bengal photoredox catalyst. The strategy efficiently prepares various a-tertiary amino acids in a single chemical step as a single enantiomer. UV–vis spectroscopy studies reveal a ternary interaction between the pyridinium salt, protein, and photocatalyst, which we hypothesize is responsible for localizing radical formation to the active site. This method highlights the opportunity for combining photoredox catalysts with enzymes to reveal new catalytic functions for known enzymes.

Abstract The transformation of a large‐volume industrial by‐product and stable greenhouse gas fluoroform (HCF 3 ) to useful products has recently received significant attention. Now, a simple and scalable preparation of AgCF 3 by treatment of HCF 3 with t ‐BuOK and AgOAc is disclosed. The reactivity of the HCF 3 ‐derived AgCF 3 has been demonstrated by hydrotrifluoromethylation of alkenes and C−H trifluoromethylation of (hetero)arenes. This work not only provides a new avenue for the utilization of HCF 3 , but also presents a reliable and easy‐to‐execute synthesis of the relatively stable AgCF 3 solution.

Fluorine and nitrogen form a successful partnership in organic synthesis, medicinal chemistry, and material sciences. Although fluorine-nitrogen chemistry has a long and rich history, this field has received increasing interest and made remarkable progress over the past two decades, driven by recent advancements in transition metal and organocatalysis and photochemistry. This review, emphasizing contributions from 2015 to 2023, aims to update the state of the art of the synthesis and applications of nitrogen-based organofluorine functional molecules in organic synthesis and medicinal chemistry. In dedicated sections, we first focus on fluorine-containing reagents organized according to the type of fluorine-containing groups attached to nitrogen, including N-F, N-RF, N-SRF, and N-ORF. This review also covers nitrogen-linked fluorine-containing building blocks, catalysts, pharmaceuticals, and agrochemicals, underlining these components’ broad applicability and growing importance in modern chemistry.