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Creators/Authors contains: "Mannodi-Kanakkithodi, Arun"

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  1. Free, publicly-accessible full text available July 1, 2024
  2. Free, publicly-accessible full text available October 1, 2023
  3. Abstract

    Visible‐light‐driven C−C bond formation utilizing ketyl radical (Cketyl) species has attracted increasing attention recently, as it provides a direct route for the synthesis of complex molecules. However, the most‐developed homogeneous photocatalytic systems for the generation and utilization of ketyl radicals usually entail noble metal‐based (e. g., Ru and Ir) photosensitizers, which suffer from not only high cost but also potential degradation and hence pose challenges in product separation and purification. In contrast, readily accessible, inexpensive, and recyclable semiconductors represent a class of attractive and alternative photocatalysts but remain much less explored for photocatalytic ketyl radical initiated C−C bond formation. This work demonstrates that a wide range of industrially important chemicals, including substituted chromanes and tertiary alcohols, can be produced on ZnIn2S4under visible light irradiation through intramolecular cyclization (Cketyl−Csp2) and intermolecular cross‐coupling (Cketyl−Csp3) reactions, respectively, using ketyl radicals. A suite of experimental studies aided by computational investigation were carried out to shed light on the mechanistic insights of these two types of ketyl radical initiated C−C coupling reactions on ZnIn2S4.

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  4. Abstract

    Deuterium (D) labeling is of great value in organic synthesis, pharmaceutical industry, and materials science. However, the state‐of‐the‐art deuteration methods generally require noble metal catalysts, expensive deuterium sources, or harsh reaction conditions. Herein, noble metal‐free and ultrathin ZnIn2S4(ZIS) is reported as an effective photocatalyst for visible light‐driven reductive deuteration of carbonyls to produce deuterated alcohols using heavy water (D2O) as the sole deuterium source. Defective two‐dimensional ZIS nanosheets (D‐ZIS) are prepared in a surfactant assisted bottom‐up route exhibited much enhanced performance than the pristine ZIS counterpart. A systematic study is carried out to elucidate the contributing factors and it is found that the in situ surfactant modification enabled D‐ZIS to expose more defect sites for charge carrier separation and active D‐species generation, as well as high specific surface area, all of which are beneficial for the desirable deuteration reaction. This work highlights the great potential in developing low‐cost semiconductor‐based photocatalysts for organic deuteration in D2O, circumventing expensive deuterium reagents and harsh conditions.

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