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BACKGROUND AND AIMS: Excise taxes represent one of the most cost-effective policies to reduce the harmful use of alcohol. Existing information about their design is limited and no standardized metric has been used to compare tax levels in the Region of the Americas. This study aimed to compare alcohol excise tax policies across the Americas, compare tax levels, and consider opportunities to improve the impact of excise taxes on alcohol consumption and health. DESIGN AND SETTING: Descriptive analysis using a method developed by the Pan American Health Organization and adapted from the World Health Organization's tobacco tax monitoring. Data were collected by surveying ministries of finance and reviewing tax legislation in effect as of November 2020 in the Region of the Americas. MEASUREMENTS: Tax policy design indicators, taxes as a percentage of the retail price of the most sold brand of beer, wine, and spirits, including a weighted average indicator across beverage types, and tax levels per standard drink (10 g ethanol) in international dollars at purchasing power parity. FINDINGS: Thirty-three countries in the Americas (94%) apply excise taxes on alcoholic beverages, with Argentina and Uruguay not applying them to wine. There is significant heterogeneity in excise tax design across countries and beverage types. Only a third of amount-specific excise taxes are regularly adjusted to avoid erosion. Regional median excise taxes represent the highest share of the price for spirits (21.4%) and the lowest for wine (11.0%). The regional median consumption-weighted average excise tax share across all beverage types is 12.0%. Excise tax shares are generally higher in Latin America than in the Caribbean and Canada. Excise tax levels per standard drink are generally lower for spirits than for other beverages. CONCLUSIONS: Alcohol excise tax policies vary significantly across the Americas, often reflecting national consumption patterns. To maximize their public health impact, tax rates could be increased, and tax designs improved, particularly to ensure higher tax burdens on high-strength drinks.

Se describe el estado actual y los avances en la aplicación de las medidas de control del tabaco contenidas en la Estrategia y Plan de Acción para Fortalecer el Control del Tabaco en la Región de las Américas 2018-2022 y se identifican los logros alcanzados entre los años 2016 y 2020 y los retos que aún se deben enfrentar para cumplir las metas previstas. Para ello se utilizaron los datos del Informe de la Organización Mundial de la Salud (OMS) sobre la Epidemia Mundial de Tabaquismo de los años 2015, 2017 y 2019, así como las normativas nacionales para determinar su consistencia con los criterios de la OMS. Se constatan importantes avances en la aplicación del Convenio Marco de la OMS para el Control del Tabaco en las Américas. Al 2020, la mayoría de los países contaban con normativas sobre ambientes 100% libres de humo en lugares cerrados públicos y de trabajo, y el transporte público, y advertencias sanitarias gráficas grandes en los paquetes de tabaco. Desde el 2016 se duplicó el número de países que prohíben la publicidad, la promoción y el patrocinio del tabaco y que aplican impuestos al tabaco al nivel mínimo recomendado por la OMS. Sin embargo, aún no se ha alcanzado la meta prevista al 2022 para ninguna de esas medidas ni para la ratificación de los tratados internacionales en el tema. Aunque se ha avanzado en la Región, el avance no ha sido uniforme, y a menos que el ritmo de aplicación de las medidas de control del tabaco contenidas en la Estrategia y Plan de Acción se acelere, es poco probable que se logren las metas establecidas. La interferencia de la industria tabacalera se mantiene como uno de los principales retos.

Spin hyperpolarization enables real-time metabolic imaging of carbon-13-labeled substrates. While hyperpolarized l-(1

This report describes the current status of the tobacco control measures contained in the Strategy and Plan of Action to Strengthen Tobacco Control in the Region of the Americas 2018-2022 (Pan American Health Organization) and the advances made in its application, identifying achievements from 2016 to 2020 and challenges that still need to be addressed in order to reach the expected goals. This analysis relied on data from the World Health Organization (WHO) Report on the Global Tobacco Epidemic from 2015, 2017, and 2019, and national regulations were analyzed to determine their consistency with WHO criteria. Significant progress has been made in implementation of the WHO Framework Convention on Tobacco Control in the Americas. By 2020, most countries had regulations on 100% smoke-free environments in indoor public places, workplaces, and public transport, and large graphic health warnings on tobacco packaging. The number of countries that ban tobacco advertising, promotion, and sponsorship and that tax tobacco at the minimum level recommended by WHO has doubled since 2016. However, the 2022 targets have not yet been reached for any of these measures or for ratification of the relevant international agreements. Although progress has been made in the Region, it has not been uniform. Unless the pace of application of the tobacco control measures contained in the Strategy and Plan of Action accelerates, it is unlikely that its targets will be met. Tobacco industry interference remains one of the main challenges.Este artigo descreve a situação atual e o progresso na implementação das medidas para o controle do tabagismo prescritas na Estratégia e plano de ação para fortalecer o controle do tabagismo na Região das Américas 2018-2022, reconhece as conquistas realizadas no período entre 2016 e 2020, e identifica os desafios a serem enfrentados para alcançar as metas planejadas. A análise se baseou em dados obtidos do Relatório da OMS sobre a Epidemia Global do Tabaco, publicado em 2015, 2017 e 2019, e em regulamentações nacionais para determinar o cumprimento dos critérios da OMS. Observam-se avanços na implementação da Convenção-Quadro da OMS para o Controle do Tabaco nas Américas. Em 2020, a maior parte dos países dispunha de regulamentações para ambientes 100% livres da fumaça do tabaco em locais públicos fechados, locais fechados de trabalho e meios de transporte público, e advertências sanitárias com ilustrações gráficas grandes nas embalagens dos produtos de tabaco. O número de países que proíbem publicidade, promoção e patrocínio do tabaco e adotaram impostos sobre os produtos do tabaco no padrão mínimo recomendado pela OMS dobrou desde 2016. No entanto, as metas planejadas para 2022 ainda não foram atingidas – tanto em relação a estas medidas quanto à ratificação dos respectivos tratados internacionais. Apesar dos avanços, o progresso na Região não é uniforme. Se as medidas para o controle do tabaco prescritas na Estratégia e plano de ação não forem implementadas em um ritmo acelerado, as metas dificilmente serão alcançadas. A interferência da indústria do tabaco continua sendo um dos maiores desafios.

To characterize the design of excise taxes on sugar-sweetened beverages (SSBs) in Latin America and the Caribbean and assess opportunities to increase their impact on SSB consumption and health.A comprehensive search and review of the legislation in effect as of March 2019, collected through existing Pan American Health Organization and World Health Organization monitoring tools, secondary sources, and surveying ministries of finance. The analysis focused on the type of products taxed, and the structure and base of these excise taxes.Out of the 33 countries analyzed, 21 apply excise taxes on SSBs. Seven countries also apply excise taxes on bottled water and at least four include sugar-sweetened milk drinks. Ten of these excise taxes are ad valorem with some tax bases set early in the value chain, seven are amount-specific, and four have either a combined or mixed structure. Three countries apply excise taxes based on sugar concentration.While the number of countries applying excise taxes on SSBs is promising, there is great heterogeneity in design in terms of structure, tax base, and products taxed. Existing excise taxes could be further leveraged to improve their impact on SSB consumption and health by including all categories of SSBs, excluding bottled water, and relying more on amount-specific taxes regularly adjusted for inflation and possibly based on sugar concentration. All countries would benefit from additional guidance. Future research should aim to address this gap.Caracterizar o modelo dos impostos especiais de consumo sobre bebidas açucaradas na América Latina e no Caribe e avaliar oportunidades para aumentar o impacto desses impostos no consumo de bebidas açucaradas e na saúde.Realizou-se uma pesquisa ampla e a análise de legislações vigentes em março de 2019, com informações obtidas por meio de instrumentos de monitoramento da Organização Pan-Americana da Saúde (OPAS) e da Organização Mundial da Saúde (OMS) já existentes, fontes secundárias e levantamento junto aos ministérios da Fazenda. A análise centrou-se no tipo de produtos tributados e na estrutura e base desses impostos especiais de consumo.Dos 33 países analisados, 21 aplicam impostos especiais de consumo sobre bebidas açucaradas. Em sete países os impostos especiais de consumo incidem também sobre água engarrafada e, em pelo menos quatro, incluem bebidas lácteas açucaradas. Dez desses tributos especiais são ad valorem com algumas bases tributárias estabelecidas no início da cadeia de valor, sete são de tipo específico e quatro têm uma estrutura combinada ou mista. Em três países os impostos especiais são estabelecidos com base na concentração de açúcares do produto.Apesar do número promissor de países com impostos especiais de consumo sobre bebidas açucaradas, verifica-se grande heterogeneidade nos modelos de tributação em termos de estrutura, base tributária e produtos tributados. Os impostos especiais de consumo vigentes poderiam ser mais bem aproveitados para aumentar o impacto no consumo de bebidas açucaradas e na saúde: incluir todas as categorias de bebidas açucaradas, excluir água engarrafada e recorrer mais a impostos de tipo específico com a correção periódica pela inflação e, possivelmente, com base na concentração de açúcares do produto. Todos os países se beneficiariam em receber mais orientação. Pesquisas futuras devem ter como objetivo abordar essa lacuna.

Deuteration of bioactive molecules is gaining more and more attention, especially after the approval of the first deuterated drug (Austedo™) by the US Food and Drug Administration (FDA). Not only is deuteration important for drug development, the amount of deuterium in a molecule is critical for the production of standards in mass spectrometry and the selectivity of the deuteration is mandatory for NMR applications. Very frequently, the molecules involved in these applications contain several heteroatoms. It has been demonstrated that oxygen-, nitrogen-, and more recently, sulfur-containing molecules can be easily deuterated at the α position leading to high deuterium incorporation. In this review we will focus our attention on the historical background and the recent progress made on heteroatom-directed deuteration, with particular attention on the catalysts and the mechanisms that drive such transformations.1 Introduction2 Oxygen-Directed Deuteration3 Nitrogen-Directed Deuteration4 Sulfur-Directed Deuteration5 Conclusion

Objetivo. Caracterizar el diseño de los impuestos selectivos al consumo de bebidas azucaradas en América Latina y el Caribe, y evaluar las oportunidades de aumentar su impacto en el consumo y la salud. Métodos. Se llevó a cabo una búsqueda y una evaluación exhaustivas de legislaciones vigentes a marzo del 2019, recopiladas mediante las herramientas de seguimiento ya existentes de la Organización Panamericana de la Salud y de la Organización Mundial de la Salud, fuentes secundarias, así como mediante una encuesta a ministerios de finanzas. El análisis se centró en el tipo de productos gravados y la estructura y la base de estos impuestos selectivos. Resultados. De los 33 países evaluados, en 21 se aplican impuestos selectivos al consumo de bebidas azucaradas. En siete países también se aplican impuestos selectivos sobre el agua embotellada y en al menos cuatro, se aplican tales impuestos sobre las bebidas lácteas azucaradas. Diez de estos impuestos selectivos al consumo son de tipo ad valorem con algunas bases imponibles fijadas en las primeras etapas de la cadena de valor, siete son de tipo específico y cuatro son de estructura combinada o mixta. En tres países se aplican impuestos selectivos al consumo en función de la concentración de azúcares del producto. Conclusiones. Si bien el número de países en que se aplican impuestos selectivos al consumo de bebidas azucaradas es prometedor, existe una gran heterogeneidad en su diseño en cuanto a la estructura, la base imponible y los productos gravados. Se podrían aprovechar aún más los impuestos selectivos existentes para tener un mayor impacto sobre el consumo de bebidas azucaradas y la salud si se incluyeran todas las categorías de bebidas azucaradas, excluyendo el agua embotellada, y si se recurriera más a impuestos específicos ajustados regularmente según la inflación y basados posiblemente en la concentración de azúcares del producto. Todos los países se beneficiarían si hubiera mayor orientación. Futuras investigaciones deberían tener como objetivo abordar esta brecha.

A stereoretentive deuteration of amino acids and amines has been developed using ruthenium on carbon catalyst, hydrogen gas at atmospheric pressure, and deuterium oxide as a source of deuterium. The process was successfully scaled-up, avoiding the use of expensive and sensitive catalyst and avoiding the use of deuterium gas under pressure. High deuterium incorporation and high yield of labeled compounds were obtained by a simple filtration process.

To characterize the design of excise taxes on sugar-sweetened beverages (SSBs) in Latin America and the Caribbean and assess opportunities to increase their impact on SSB consumption and health.A comprehensive search and review of the legislation in effect as of March 2019, collected through existing Pan American Health Organization and World Health Organization monitoring tools, secondary sources, and surveying ministries of finance. The analysis focused on the type of products taxed, and the structure and base of these excise taxes.Out of the 33 countries analyzed, 21 apply excise taxes on SSBs. Seven countries also apply excise taxes on bottled water and at least four include sugar-sweetened milk drinks. Ten of these excise taxes are ad valorem with some tax bases set early in the value chain, seven are amount-specific, and four have either a combined or mixed structure. Three countries apply excise taxes based on sugar concentration.While the number of countries applying excise taxes on SSBs is promising, there is great heterogeneity in design in terms of structure, tax base, and products taxed. Existing excise taxes could be further leveraged to improve their impact on SSB consumption and health by including all categories of SSBs, excluding bottled water, and relying more on amount-specific taxes regularly adjusted for inflation and possibly based on sugar concentration. All countries would benefit from additional guidance. Future research should aim to address this gap.Caracterizar el diseño de los impuestos selectivos al consumo de bebidas azucaradas en América Latina y el Caribe, y evaluar las oportunidades de aumentar su impacto en el consumo y la salud.Se llevó a cabo una búsqueda y una evaluación exhaustivas de legislaciones vigentes a marzo del 2019, recopilada mediante las herramientas de seguimiento ya existentes de la Organización Panamericana de la Salud y de la Organización Mundial de la Salud, fuentes secundarias, así como mediante una encuesta a ministerios de finanzas. El análisis se centró en el tipo de productos gravados y la estructura y la base de estos impuestos selectivos.De los 33 países evaluados, en 21 se aplican impuestos selectivos al consumo de bebidas azucaradas. En siete países también se aplican impuestos selectivos al consumo de agua embotellada y en al menos cuatro, se incluyen las bebidas lácteas azucaradas. Diez de estos impuestos selectivos al consumo son de tipoSi bien el número de países en que se aplican impuestos selectivos al consumo de bebidas azucaradas es prometedor, existe una gran heterogeneidad en su diseño en cuanto a la estructura, la base imponible y los productos gravados. Se podrían aprovechar aún más los impuestos selectivos existentes a fin de que tengan un mayor impacto sobre la salud y el consumo si se incluyen todas las categorías de bebidas azucaradas, excluyendo el agua embotellada, y recurriendo más a impuestos de tipo específico ajustados frecuentemente según la inflación y basados posiblemente en la concentración de azúcares del producto. Todos los países se beneficiarían si hubiera mayor orientación. Las próximas investigaciones deberían abordar esta brecha.Caracterizar o modelo dos impostos especiais de consumo sobre bebidas açucaradas na América Latina e no Caribe e avaliar oportunidades para aumentar o impacto desses impostos no consumo de bebidas açucaradas e na saúde.Realizou-se uma pesquisa ampla e a análise de legislações vigentes em março de 2019, com informações obtidas por meio de instrumentos de monitoramento da Organização Pan-Americana da Saúde (OPAS) e da Organização Mundial da Saúde (OMS) já existentes, fontes secundárias e levantamento junto aos ministérios da Fazenda. A análise centrou-se no tipo de produtos tributados e na estrutura e base desses impostos especiais de consumo.Dos 33 países analisados, 21 aplicam impostos especiais de consumo sobre bebidas açucaradas. Em sete países os impostos especiais de consumo incidem também sobre água engarrafada e, em pelo menos quatro, incluem bebidas lácteas açucaradas. Dez desses tributos especiais sãoApesar do número promissor de países com impostos especiais de consumo sobre bebidas açucaradas, verifica-se grande heterogeneidade nos modelos de tributação em termos de estrutura, base tributária e produtos tributados. Os impostos especiais de consumo vigentes poderiam ser mais bem aproveitados para aumentar o impacto no consumo de bebidas açucaradas e na saúde: incluir todas as categorias de bebidas açucaradas, excluir água engarrafada e recorrer mais a impostos de tipo específico com a correção periódica pela inflação e, possivelmente, com base na concentração de açúcares do produto. Todos os países se beneficiariam em receber mais orientação. Pesquisas futuras devem ter como objetivo abordar essa lacuna.

A new three-component assembly reaction between N-tosylhydrazones, dihalogenated arenes, and boronic acids or boronate esters was developed, producing highly substituted 1,1-diarylethylenes in good yields. The two C-C bonds formed through this coupling have been catalyzed by a single Pd-catalyst in a one-pot fashion. It is noted that the one-pot pinacol boronate cross-coupling reaction generally provides products in high yields, offers an expansive substrate scope, and can address a broad range of aryl, styrene, vinyl, and heterocyclic olefinic targets. The scope of this one-pot coupling has been also extended to the synthesis of the 1,1-diarylethylene skeleton of the natural product ratanhine. The new compounds were evaluated for their cytotoxic activity, and this allowed the identification of compound 4ab that exhibits excellent antiproliferative activity in the nanomolar concentration range against HCT116 cancer cell lines.

New approaches to the Pd-catalysis employing palladacycle precatalysts have been recently developed. Breakthroughs in this area using 2-aminobiphenyl palladacycle precatalysts are highlighted. High reactivity and selectivity are achieved for the C–C and C–heteroatom bond formation under mild reaction conditions.

International audience; The synthesis of amino-substituted N-vinylazoles was achieved by a new palladium-assisted tandem catalytic reaction involving N-tosylhydrazones, halo-substituted azoles, and amines. Accordingly, two Csp(2)-N bonds were formed through two mechanistically distinct reactions using a single Pd(II)/Pd(0) catalyst system in a one-pot fashion. This work paves the way for the design of biological relevant compounds in an amino-substituted N-vinylindole series. Among several polyoxygenated derivatives evaluated, compounds 5e and 5u were found to exhibit good antiproliferative activity.

The reactivity of sterically hindered N-tosylhydrazones 2 featuring ortho/ortho'-substituents on the aromatic ring with various ortho-, meta-, and para-substituted aryl halides 3 was investigated. To accomplish successfully this challenging coupling, fine-tuning of the reaction conditions were required. The newly established PdCl(2)(MeCN)(2)/Xphos/NaO-t-Bu/F-benzene system in a sealed tube is compatible with a broad spectrum of both coupling partners, regardless of their electronic and steric nature. This protocol has been applied successfully to the synthesis of a xanthene derivative.

A new three-component assembly reaction between N-tosylhydrazones, dihalogenated arenes, and boronic acids or boronate esters was developed, producing highly substituted 1,1-diarylethylenes in good yields. The two C–C bonds formed through this coupling have been catalyzed by a single Pd-catalyst in a one-pot fashion. It is noted that the one-pot pinacol boronate cross-coupling reaction generally provides products in high yields, offers an expansive substrate scope, and can address a broad range of aryl, styrene, vinyl, and heterocyclic olefinic targets. The scope of this one-pot coupling has been also extended to the synthesis of the 1,1-diarylethylene skeleton of the natural product ratanhine. The new compounds were evaluated for their cytotoxic activity, and this allowed the identification of compound 4ab that exhibits excellent antiproliferative activity in the nanomolar concentration range against HCT116 cancer cell lines.

A general and efficient protocol for the palladium-catalyzed functionalization of mono- and polyglycosyl thiols by using the palladacycle precatalyst G3-XantPhos was developed. The CS bond-forming reaction was achieved rapidly at room temperature with various functionalized (hetero)aryl-, alkenyl-, and alkynyl halides. The functional group tolerance on the electrophilic partner is typically high and anomer selectivities of thioglycosides are high in all cases studied. New sulfur nucleophiles such as thiophenols, alkythiols, and thioaminoacids (cysteine) were also successfully coupled to lead to the most general and practical method yet reported for the functionalization of thiols.

New approaches to the Pd-catalysis employing palladacycle precatalysts have been recently developed. Breakthroughs in this area using 2-aminobiphenyl palladacycle precatalysts are highlighted. High reactivity and selectivity are achieved for the C–C and C–heteroatom bond formation under mild reaction conditions.

Conducting polymer based hybrid materials were synthesized by a new route. The use of pyrrole derivatives functionalized by a carboxylic acid or beta-diketone group allows to control the polymerization rate of zirconium tetrapropoxide (Zr(OPr)(4)). The organic species entrapped in the resulting hybrid materials yield conducting polymers by electropolymerization. The results show that the formation of the conducting polymers depends on the nature of the monomer. Moreover, the presence of polysiloxane chains within the hybrid materials improves the properties of the latter.

Two Csp2—N bonds are formed through two mechanistically distinct reactions in a one-pot fashion.

We describe the preparation of new hybrid materials using a novel method previously reported by us. These materials are constituted of an organic part and an inorganic network of silicon and zirconium oxopolymers. The organic polymer is obtained by electropolymerization of an N-functionalized pyrrole entrapped in the xerogel. The latter was obtained from a sol prepared by hydrolysis condensation of a mixture of alkoxysilanes, zirconium alkoxydes and the organic monomer. The chemical and electrochemical conditions to prepare these hybrid materials were investigated by varying the zirconium content, the presence and the nature of doping species in the xerogel, the nature of the electrolytic salt and the hydrolysis catalyst. From the results of cyclic voltammetry, optical microscopy, scanning electron microscopy and X-ray fluorescence, we show that the formation of a conducting polymer with good properties in the xerogel depends on the zirconium content and on both the nature and the presence of doping species in the xerogel, whereas the influence of the electrolytic salt is very limited.

In order to improve the anticorrosion protection properties of polypyrrole (PPy) films deposited on iron or mild steel, the organic conductive polymer was covered by a thermally and mechanically resistant xerogel layer. The anticorrosion protective effect of such a bilayered coating was evaluated by electrochemical measurements (i = f(E); E = f(t); polarization resistance (Rp)) in NaCl (30 g L−1) and in HCl (1 M) aqueous solutions and by analysis of NaCl and HCl aqueous solutions in which samples coated by PPy and the xerogel were immersed for one and seven days. The results were compared with those obtained, in the same conditions, for naked mild steel plates, PPy or xerogel coated mild steel plates. The bilayer coating ensures a very efficient protection of mild steel against corrosion. A synergy between PPy and the xerogel was revealed. Moreover, the weak adherence of the xerogel on PPy was improved by the incorporation in the organic polymer of carboxylic acid-functionalized pyrrole units, and the corrosion protection of these modified layers was still increased.

The synthesis and characterization of bis(salen)-type complexes are reported. Using a “template” method, bimetallic complexes as dyssymmetric ligands can easily be built, giving birth to an unprecedented class of metal Schiff-base salen complexes. Electrochemical investigations allow us to study the overoxidation process that occurs during the polymerization. Furthermore, chronoamperometry studies indicate higher kinetics of electron charge transfer as a proof of an improvement in the polymer framework.

The synthesis of pyrroles functionalized by complexing groups such as acetylacetone, dibenzoylmethane or carboxylic acids is described, as well as their electrooxidation into functionalized polypyrroles. We have studied the behavior of poly(functionalized pyrrole) films in the presence of Li+, Ni2+ and Co2+ cations by cyclic voltammetry (CV) and infrared (IR) spectroscopy. The electrochemical response under various conditions differs with the nature of the complexing group. We have also demonstrated the possibility to electrochemically generate copolymers with pyrrole and each functionalized pyrrole. The proportion of functional groups in the copolymers was estimated by following the peak potential dependence in cyclic voltammetry and was confirmed by IR spectroscopy.

New kinds of modified electrodes have been prepared on the basis of electroactive polymers containing bimetallic ‘anil’ and ‘salen’-type complexes. New tetrahydro ‘anil’ ligands and complexes have been synthesized, giving birth to a new family of electroactive polymers. The polymers have been prepared potentiostatically and exhibit electrochemical properties analogous to simple polysalens. In the case of binuclear complexes both imino- and amino-linked monomers polymerize, but the polymers exhibit quite different charge transfer dynamics. Electropolyme′risation anodique de complexes binucle′aires de type ‘anil’ et ‘salen’ et de leur de′rive′s tetrahydroge′ne′s. Un nouveau type d'e′lectrodes modifie′es a e′te′ e′labore′ sur la base de polymeres e′lectroactifs issus de complexes bime′talliques de type ‘anil’ et ‘salen’. Nous avons synthe′tise′ des ligands et complexes tetrahydro ‘anil’ originaux donnant acces a une nouvelle famille de polymeres e′lectroactifs. Les complexes binucle′aires posse′dant des liaisons imine et amine polyme′risent e′galement, mais les polymeres pre′sentent des comportements tres diffe′rents sur le plan du transfert e′lectronique.

The electrochemical oxidation of several silyl enolethers (SE) formed from a variety of differently substituted α- or β-tetralones by side chains is described. The behaviour of the cation radicals of the SE has been found to be strongly dependent on the substituted lateral chain, especially when the substituent contains a cyclizable group like a double bond. The difference between the oxidation potentials has been attibuted to the occurence of a first order chemical reaction between the cation radical and the substituent, which is probably a cyclization reaction. The relative rates of this reaction have been discussed in relation to the substituent.

The new method for the synthesis of substituted N-vinylazoles shows a broad functional group tolerance.

Broad spectrum of both coupling partners is tolerated, regardless the electronic and steric properties.

A new three-component assembly reaction between N-tosylhydrazones, dihalogenated arenes, and various primary and secondary amines was devised, producing nitrogen-containing 1,1′-diarylethylenes in good yields. The two C–C and C–N bonds formed through this coupling have been catalyzed by a single Pd-catalyst in a one-pot fashion.

The electro-oxidation of three isomeric methyl benzoxazines has been studied in acetonitrile and methanol in either neutral or alkaline media. Oxidation potentials have been determined and the reactivity of the benzoxazine cation radicals estimated. In alkaline methanol, the mechanism changes in favour of oxidation of the benzoxazine anion, and formation of a thin polymer layer is observed on metallic substrates. The resulting polymers were analysed by X-ray photoelectron spectroscopy measurements and a polymer formula has been proposed.

A new three-component assembly reaction between N-tosylhydrazones, dihalogenated arenes, and various primary and secondary amines was devised, producing nitrogen-containing 1,1′-diarylethylenes in good yields. The two C–C and C–N bonds formed through this coupling have been catalyzed by a single Pd-catalyst in a one-pot fashion.

A general synthesis of derivatives of 1,2,4-triphenyl-4,10-dihydro-10-thia-3,4-diazaphenanthrene (a new heterocyclic skeleton) in two steps from 3-arylidene-4-isothiochromanones via cycloaddition route is recorded.

The previously suggested mechanism of the condensation–rearrangement reaction of a Reissert compound hydrofluoroborate salt with reactive olefins was reexamined in the case of methyl methacrylate, itaconate, citraconate, and mesaconate. Addition of triethylamine to the reaction medium leads to the isolation of a presumed intermediate 8. Spectrometric (proton magnetic resonance) data of the compounds 8 allow us to specify their stereochemistry and in two cases to point out an isomerization equilibrium. Keywords: Reissert compound fluoroborate salt, [4 + 2] cycloaddition, stereochemistry.

A general synthesis of derivatives of 1,2,4-triphenyl-4,10-dihydro-10-thia-3,4-diazaphenanthrene (a new heterocyclic skeleton) in two steps from 3-arylidene-4-isothiochromanones via cycloaddition route is recorded.