Publications by authors named "T L Gianetti"
Diffusion-limited kinetics is a key mechanistic debate when consecutive photoelectron transfer (conPET) is discussed in photoredox catalysis. In-situ generated organic photoactive radicals can access catalytic systems as reducing as alkaline metals that can activate remarkably stable bonds. However, in many cases, the extremely short-lived transient nature of these doublet state open-shell species has led to debatable mechanistic studies, hindering adoption and development.
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- The report discusses a method to synthesize borazine from ammonia borane using a specific rhodium-based catalyst.
- An intermediate complex, made of dirhodium and ammonia borane, is synthesized and characterized.
- The findings offer valuable insights into how the activation process might occur during this chemical reaction.
Chromoselective bond activation has been achieved in organic helicenium (Pr-DMQA)-based photoredox catalysis. Consequently, control over chromoselective C(sp)-X bond activation in multihalogenated aromatics has been demonstrated. Pr-DMQA can only initiate the halogen atom transfer (XAT) pathway under red light irradiation to activate low-energy-accessible C(sp)-I bonds.
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- Nitrogen oxides (NO, NO2, and N2O) are significant air pollutants, and a bimetallic Rh-Pt complex can catalyze their detoxification with hydrogen, producing water and dinitrogen.
- The process occurs at room temperature and low pressures, achieving a remarkable turnover number of 587 for converting N2O, making it the best catalyst for this reaction.
- Detailed investigations into the reaction mechanism using NMR and DFT calculations reveal a stepwise hydrogenation process, involving intermediates like hyponitrite (N2O2) during the conversion of NO to N2.
A red-light-mediated Pr-DMQA-catalyzed cascade intramolecular trifluoromethylation and dearomatization of indole derivatives with Umemoto's reagent has been developed. This protocol provides a facile and efficient approach for the construction of functionalized and potentially biologically important CF-containing 3,3-spirocyclic indolines with moderate to high yields and excellent diastereoselectivities under mild conditions. The success of multiple gram-scale (1 and 10 g) experiments further highlights the robustness and practicality of this protocol and the merit of the employment of red light.
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