Robust and Self-Cleaning Electrochemical Production of Periodate.

Periodate, a platform oxidizer, can be electrochemically recycled in a self-cleaning process. Electrosynthesis of periodate is well established at boron-doped diamond (BDD) anodes. However, recovered iodate and other iodo species for recycling can contain traces of organic impurities from previous applications. For the first time, it was shown that the organic impurities do not hamper the electrochemical re-oxidation of used periodate. In a hydroxyl-mediated environment, the organic compounds form CO2 and H2 O during the degradation process. This process is often referred to as "cold combustion" and provides orthogonal conditions to periodate synthesis. To demonstrate the strategy, different dyes, pharmaceutically active ingredients, and iodine compounds were added as model contaminations into the process of electrochemical periodate production. UV/Vis spectroscopy, NMR spectroscopy, and mass spectrometry (MS) were used to monitor the degradation of organic molecules, and liquid chromatography-MS was used to control the purity of periodate. As a representative example, dimethyl 5-iodoisophthalate (2 mm), was degraded in 90, 95, and 99 % while generating 0.042, 0.054, and 0.082 kilo equiv. of periodate, respectively. In addition, various organic iodo compounds could be fed into the periodate generation for upcycling such iodo-containing waste, for example, contrast media.

Electrochemical Installation of CFH2 -, CF2 H-, CF3 -, and Perfluoroalkyl Groups into Small Organic Molecules.

Electrosynthesis can be considered a powerful and sustainable methodology for the synthesis of small organic molecules. Due to its intrinsic ability to generate highly reactive species under mild conditions by anodic oxidation or cathodic reduction, electrosynthesis is particularly interesting for otherwise challenging transformations. One such challenge is the installation of fluorinated alkyl groups, which has gained significant attention in medicinal chemistry and material science due to their unique physicochemical features. Unsurprisingly, several electrochemical fluoroalkylation methods have been established. In this review, we survey recent developments and established methods in the field of electrochemical mono-, di-, and trifluoromethylation, and perfluoroalkylation of small organic molecules.

Metal-Free Photoinduced Hydroalkylation Cascade Enabled by an Electron-Donor-Acceptor Complex.

A metal- and photocatalyst-free photoinduced radical cascade hydroalkylation of 1,7-enynes has been disclosed. The process is triggered by a single electron transfer (SET) event involving a photoexcited electron-donor-acceptor complex between an NHPI ester and a Hantzsch ester, which decomposes to afford a tertiary radical that is readily trapped by the enyne. The method provides an operationally simple, robust, and step-economical approach toward the construction of diversely functionalized dihydroquinolinones bearing quaternary centers. A sequential one-pot hydroalkylation-isomerization approach is also offered, giving access to a family of quinolinones. A wide substrate scope and high functional group tolerance were observed in both approaches.

Photoredox Catalysis toward 2-Sulfenylindole Synthesis through a Radical Cascade Process.

A radical cascade process initiated through visible-light induced thiyl radical coupling with ortho-substituted arylisocianides followed by an intramolecular cyclization and subsequent aromatization to access 2-sulfenylindoles is described. The key thiyl radicals are promptly generated via a hydrogen atom transfer event. The redox-neutral protocol features broad substrate scope, excellent functional group tolerance, and mild reaction conditions. Furthermore, the implementation of a continuous flow variant allows smooth scalability with a short residence time through process intensification.

Production of chiral compounds using immobilized cells as a source of biocatalysts.

The importance of chiral compounds in all fields of technology and life sciences is shown. Small chiral molecules are mainly used as building blocks in the synthesis of more complex and functionalized compounds. Nature creates and imposes stereoselectivity by means of enzymes, which are highly efficient biocatalysts. The use of whole cells as a biocatalyst source is a promising strategy for avoiding some drawbacks associated with the use of pure enzymes, especially their high cost. The use of free cells is also challenging, since cell lysis can also occur under the reaction conditions. However, cell immobilization has been employed to increase the catalytic potential of enzymes by extending their lifetimes in organic solvents and non-natural environments. Besides, immobilized cells maintain their biocatalytic performance for several reaction cycles. Considering the above-mentioned arguments, several authors have synthesized different classes of chiral compounds such as alcohols, amines, carboxylic acids, amides, sulfides and lactones by means of immobilized cells. Our aim was to discuss the main aspects of the production of chiral compounds using immobilized cells as a source of biocatalysts, except under fermentation conditions.

Investigating the influence of the interface in thiol-functionalized silver-gold nanoshells over lipase activity.

We employed thiol-funcionalized AgAu nanoshells (AgAu NSs) as supports for the covalent attachment of lipases (BCL, Burkholderia cepacia lipase; PPL, pancreatic porcine lipase). Specifically, we were interested in investigating the effect of the nature/size of the spacer in AgAu NSs-functionalized organic thiols over the covalent attachment of lipases. The catalytic performance of AgAu-lipase systems was measured in the kinetic resolution of (R,S)-1-(phenyl)ethanol via a transesterification reaction. In comparison to free BCL, the lipase attached to AgAu NSs using a small spacer such as cysteamine or mercaptoacetic acid, with the largest spacer mercaptoundecanoic acid, had the fastest conversion rate. The recycling potential for BCL was investigated. After three reaction cycles, the enzyme activity was kept at around 90% of the initial value. The results described herein show that the size of the spacer plays an important role in optimizing lipase activities in metallic nanoshells as solid supports.