Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering , Kyoto University, Nishikyo-ku , Kyoto 615-8510 , Japan.
Published: May 2018
AI Article Synopsis
Article Abstract
Electrochemistry serves as a powerful method for generating reactive intermediates, such as organic cations. In general, there are two ways to use reactive intermediates for chemical reactions: (1) generation in the presence of a reaction partner and (2) generation in the absence of a reaction partner with accumulation in solution as a "pool" followed by reaction with a subsequently added reaction partner. The former approach is more popular because reactive intermediates are usually short-lived transient species, but the latter method is more flexible and versatile. This review focuses on the latter approach and provides a concise overview of the current methods for the generation and accumulation of cationic reactive intermediates as a pool using modern techniques of electrochemistry and their reactions with subsequently added nucleophilic reaction partners.
Density functional theory (DFT) calculations indicate that [Co(HO)] reacts with two HO molecules to form [(HO)Co(OOH)(HO)] reactant complexes, which decompose through three distinct pathways depending on the relative orientation between the coordinated OOH and HO ligands. The reactive intermediates produced via these activation pathways include hydroperoxyl (OOH)/superoxide (O) radicals, singlet oxygen (O), and Co(III) species [(HO)Co(O)], [(HO)Co(OH)], and [(HO)Co(OH)]. The Co(III) species display from moderate to strong oxidizing abilities that have long been overlooked.
Dexter energy transfer (DET) of triplet electronic states is used to direct energy in photovoltaics, quench reactive singlet oxygen species in biological systems, and generate them in photodynamic therapy. However, the extent to which repeated DET between aromatic residues can lead to triplet energy migration in proteins has not been investigated. Here, we computationally describe DET rates in microtubules, actin filaments and the intermediate filament, vimentin.
The isoquinoline core is present in one of the largest subsets of bioactive natural products. The multifunctional isoquinoline core exerts diverse bioactivity, resulting in the development of numerous isoquinoline-based drugs and molecules that are currently under clinical trials. We developed a new approach for phosphite-mediated [1,2] alkyl migration for an overall -C-H alkylation -alkylation of isoquinoline.
The electrochemical nitrate reduction reaction (NORR) involves multiple hydrogenation and deoxygenation steps, which compete with the hydrogen evolution reaction (HER). Therefore, NORR driven in acidic media is challenging in spite of advantageous fast hydrogen transfers in its elementary steps. The findings presented in this article first demonstrate that the NORR is significantly activated even in acidic lithium nitrate solutions at LiNO concentrations exceeding 6 m on a Pt electrode (the highly effective catalyst for HER) by the formation of a "hydronium-in-salt" electrolyte (HISE), a new type of aqueous high concentration salt electrolyte.
(-)-Exiguolide is a marine macrolide natural product with potent anticancer activity. In this study, the total synthesis of exiguolide stereoisomers, (9)-exiguolide, (9,13)-exiguolide, and (9,13,19)-exiguolide, was achieved by capitalizing on our macrocyclization/transannular pyran cyclization strategy. The impact of the stereochemical permutation on the reactivity of advanced intermediates, the conformation of the macrocyclic skeleton, and the antiproliferative activity against human cancer cells were investigated in detail.
