The focus of this review is to provide an overview of the field of organocatalysed photoredox chemistry relevant to synthetic medicinal chemistry. Photoredox transformations have been shown to enable ...key transformations that are important to the pharmaceutical industry. This type of chemistry has also demonstrated a high degree of sustainability, especially when organic dyes can be employed in place of often toxic and environmentally damaging transition metals. The sections are arranged according to the general class of the presented reactions and the value of these methods to medicinal chemistry is considered. An overview of the general characteristics of the photocatalysts as well as some electrochemical data is presented. In addition, the general reaction mechanisms for organocatalysed photoredox transformations are discussed and some individual mechanistic considerations are highlighted in the text when appropriate.
Potential energy diagrams have been central tools for chemistry teaching and research for over 50 years. We present an application, EveRplot, which is accessible by web browser (including mobile ...devices) and can be used to create energy versus reaction coordinate plots quickly and easily. Through three case studies, we illustrate the use of the application for both teaching and research. In addition, we provide a handout that outlines how the application may be used in the context of a class on physical organic chemistry.
Carbon dioxide (CO2) impacts every aspect of life, and numerous sensing technologies have been established to detect and monitor this ubiquitous molecule. However, its selective sensing at the ...molecular level remains an unmet challenge, despite the tremendous potential of such an approach for understanding this molecule’s role in complex environments. In this work, we introduce a unique class of selective fluorescent carbon dioxide molecular sensors (CarboSen) that addresses these existing challenges through an activity-based approach. Besides the design, synthesis, and evaluation of these small molecules as CO2 sensors, we demonstrate their utility by tailoring their reactivity and optical properties, allowing their use in a broad spectrum of multidisciplinary applications, including atmospheric sensing, chemical reaction monitoring, enzymology, and live-cell imaging. Collectively, these results showcase the potential of CarboSen sensors as broadly applicable tools to monitor and visualize carbon dioxide across multiple disciplines.
Carbon dioxide (CO
) impacts every aspect of life, and numerous sensing technologies have been established to detect and monitor this ubiquitous molecule. However, its selective sensing at the ...molecular level remains an unmet challenge, despite the tremendous potential of such an approach for understanding this molecule's role in complex environments. In this work, we introduce a unique class of selective fluorescent carbon dioxide molecular sensors (CarboSen) that addresses these existing challenges through an activity-based approach. Besides the design, synthesis, and evaluation of these small molecules as CO
sensors, we demonstrate their utility by tailoring their reactivity and optical properties, allowing their use in a broad spectrum of multidisciplinary applications, including atmospheric sensing, chemical reaction monitoring, enzymology, and live-cell imaging. Collectively, these results showcase the potential of CarboSen sensors as broadly applicable tools to monitor and visualize carbon dioxide across multiple disciplines.
Many methods report the scission of N–O bonds of aromatic heterocycles and their subsequent functionalization. Oxidative addition is one of the presumed pathways through which aromatic N–O bond ...activation with transition metals is achieved. We report the first well-defined pathway of (benz)isoxazole’s aromatic N–O bond activation through oxidative addition. We also provide control experiments, which show that aromatic N–O bonds may be broken by strong inorganic reductants. These results highlight that N–O bonds are susceptible to both reduction and oxidative addition, which has important implications for catalysis. Exploring the reactivity of one of these complexes toward a series of electrophiles leads to the discovery of a Staudinger-type β-lactam synthesis upon the reaction with a ketene. Finally, we demonstrate that the choice of different metal/ligand combinations allows for selective oxidative addition into either C–I bonds or N–O bonds in the presence of the other.
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