Sulfur dioxide electrocatalysis of radical-chain trifluoromethylation of thiophenols by bromotrifluoromethane

The possibility of electrocatalysis by sulfur dioxide has been demonstrated in the trifluoromethylation of thiophenols by Freon F13B1 (CF₃Br) to form trifluoromethyl aryl sulfides. A study has been made of the influence of the mediator concentration, the electronic structure of the thiophenol, and the electrolysis conditions on the course of the trifluoromethylation process.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 29, No. 3, pp. 244–249, May–June, 1993.The authors wish to express their appreciation to the State Committee of the Ukraine on Matters of Science and Technology, for financial support of this work within the scope of the Fundamental Research Fund.     

Perfluoroethanesulfonyl fluoride: Preparation from sultone

A procedure was developed for preparing perfluoroethanesulfonyl fluoride by synthesis of hexafluoropropane-2-β-sultone from sulfuric anhydride and perfluoropropene, followed by hydrolysis of the sultone to α-tetrafluoroethanesulfonyl fluoride and fluorination of the latter with elemental fluorine.     

Bis-para-semiquinoid type double cyclopalladation in the series of six-membered two-nitrogen bridged annulene-dihydroannulene ligands

The cyclometallation reaction known in the series of annulene heteroorganic ligands was extended to six-membered dihydroannulenes with a dinitrogen bridge. Double cyclopalladation of 4-methyl-4-trichloromethylcyclohexa-2,5-dien-1-one azine yielded the first representative of a new class of cross-conjugated diazadipalladatetracycles,viz., 5,10-bis(acetylacetonato)-2,7-dimethyl-2,7-bis(trichloromethyl)-2,7-dihydro-4b,9b-diaza-5,10-dipalladaindeno[2,1-a]indene, isolated as a diastereomer mixture of the achiralmeso-form (E-isomer) and a racemate (Z-isomer). This reaction offers a method for transition metal-mediated activation of non-reactive C−H bonds at position 2 of cyclohexa-2,5-dienylidene systems and a route toward the very rare chiral polyheteroelement system with rotational symmetry. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1236–1239, June, 1997.     

Light‐Gated Synthetic Protocells for Plasmon‐Enhanced Chemiosmotic Gradient Generation and ATP Synthesis

Herein, we present a light‐gated protocell model made of plasmonic colloidal capsules (CCs) assembled with bacteriorhodopsin for converting solar energy into electrochemical gradients to drive the synthesis of energy‐storage molecules. This synthetic protocell incorporated an important intrinsic property of noble metal colloidal particles, namely, plasmonic resonance. In particular, the near‐field coupling between adjacent metal nanoparticles gave rise to strongly localized electric fields and resulted in a broad absorption in the whole visible spectra, which in turn promoted the flux of photons to bacteriorhodopsin and accelerated the proton pumping kinetics. The cell‐like potential of this design was further demonstrated by leveraging the outward pumped protons as “chemical signals” for triggering ATP biosynthesis in a coexistent synthetic protocell population. Hereby, we lay the ground work for the engineering of colloidal supraparticle‐based synthetic protocells with higher‐order functionalities.     

Synthesis of ferrocene annulated trifluoromethylated heterocycles with crispine and lamellarin skeletons

Ferrocene analogues of pyrrolo[2,1-a]isoquinoline alkaloids, 2-(trifluoromethyl)-5,6-dihydroferroceno[g]indolizine and 6-(trifluoromethyl)-8,9-dihydro-6H-chromeno[4,3-b]ferroceno[g]indolizines, were obtained in 44–65% yield via the Grob reaction between 1-nitro-1-(2,2,2-trifluoroethylidene)alkanes or 3-nitro-2-(trifluoromethyl)-2H-chromenes and 1-alkyl-3,4-dihydroferroceno[c]pyridines in 2-propanol at reflux.