Facile synthesis of diiodoheteroindenes and understanding their Sonogashira cross-coupling selectivity for the construction of unsymmetrical enediynes.

Electrophile-promoted cyclizations of functionalized alkynes offer a useful tool for constructing halogen-substituted heterocycles primed for further derivatization. Preinstallation of an iodo-substituent at the alkyne prior to iodo-cyclization opens access to ortho di-iodinated heterocyclic precursors for the preparation of unsymmetrical heterocycle-fused enediynes. This general approach was used to prepare 2,3-diiodobenzothiophene, 2,3-diiodoindole, and 2,3-diiodobenzofuran, a useful family of substrates for systematic studies of the role of heteroatoms on the regioselectivity of cross-coupling reactions. Diiodobenzothiophene showed much higher regioselectivity for Sonogashira cross-coupling at C2 than diiodoindole and diiodobenzofuran. As a result, benzothiophene can be conveniently involved in a one-pot sequential coupling with two different alkynes, yielding unsymmetrical benzothiophene-fused enediynes. On the other hand, the Sonogashira reaction of diiodoindole and diiodobenzofuran formed considerable amounts of di-substituted enediynes in addition to the monoalkyne product by coupling at C2. Interestingly, no C3-monocoupling products were observed for all of the diiodides, suggesting that the incorporation of the 1st alkyne at C2 activates the C3 position for the 2nd coupling. Additional factors affecting regioselectivity were detected, discussed and connected, through computational analysis, to transmetalation being the rate-determining step for the Sonogashira reaction. Several enediynes synthesized showed cytotoxic activity, which is not associated with DNA strand breaks typical of natural enediyne antibiotics.

The Green Method in Water Management: Electron Beam Treatment.

During the prebiotic era, radiolytic transformations in the oceans played a key role in purifying water from toxic impurities and, thus, played a role in the formation of the aquatic environment of our planet, making it suitable for the emergence of life. Today, the planet again faces the challenge of how to provide people with clean water. Therefore, it is reasonable to look back at past historical stages and again consider the possibility of neutralizing pollutants in water by means of radiolysis, which has already been tested by time. Modern radiolytic treatments can be much faster and safer thanks to the advent of powerful electron accelerators and high-rate electron beam treatment (ELT) of water and wastewater. Radiolytic treatment of water using accelerated electrons corresponds to the essence of advanced oxidative technologies and green chemistry. The ELT of water instantly generates a high concentration of short-lived radicals that can quickly neutralize and decompose chemical and bacterial pollutants. Due to the ability of accelerated electrons to penetrate into a substance, ELT provides the decomposition of both dissolved and suspended pollutants. The cleaning effect of ELT is due to the ability to inactivate toxic and chromophore functional groups, transform impurities into an easily removable form, damage the DNA of microorganisms and their spore forms, and increase the biodegradability of organic impurities. The use of ELT in water treatment provides significant savings in chemical reagents, thereby improving quality and reducing the number of cleaning steps. The compactness, high degree of automation of the equipment used, energy efficiency, high productivity, and excellent compatibility with traditional water treatment methods are important advantages of ELT. Unlike conventional chemicals, the excess radicals generated in the ELT process are converted back to water and hydrogen; thus, the chemical and corrosive activity of water does not increase. Equipping research institutes with electron accelerators, developing cheaper accelerators, and granting government support for pilot projects are key conditions for introducing ELT into water treatment practice.

1-Iodobuta-1,3-diynes in Copper-Catalyzed Azide-Alkyne Cycloaddition: A One-Step Route to 4-Ethynyl-5-iodo-1,2,3-triazoles.

Cu-catalyzed 1,3-dipolar cycloaddition of iododiacetylenes with organic azides using iodotris(triphenylphosphine)copper(I) as a catalyst was found to be an efficient one-step synthetic route to 5-iodo-4-ethynyltriazoles. The reaction is tolerant to various functional groups in both butadiyne and azide moieties. The synthetic application of 5-iodo-4-ethynyl triazoles obtained was also evaluated: the Sonogashira coupling with alkynes resulted in unsymmetrically substituted triazole-fused enediyne systems, while the Suzuki reaction yielded the corresponding 5-aryl-4-ethynyl triazoles.

Radiation-induced high-temperature conversion of cellulose.

Thermal decomposition of cellulose can be upgraded by means of an electron-beam irradiation to produce valuable organic products via chain mechanisms. The samples being irradiated decompose effectively at temperatures below the threshold of pyrolysis inception. Cellulose decomposition resembles local "explosion" of the glucopyranose unit when fast elimination of carbon dioxide and water precede formation of residual carbonyl or carboxyl compounds. The dry distillation being performed during an irradiation gives a liquid condensate where furfural and its derivatives are dominant components. Excessively fast heating is adverse, as it results in a decrease of the yield of key organic products because pyrolysis predominates over the radiolytic-controlled decomposition of feedstock. Most likely, conversion of cellulose starts via radiolytic formation of macroradicals do not conform with each other, resulting in instability of the macroradical. As a consequence, glucosidic bond cleavage, elimination of light fragments (water, carbon oxides, formaldehyde, etc.) and formation of furfural take place.