Synthesis of 3-Carbonyl Trisubstituted Furans via Pd-Catalyzed Aerobic Cycloisomerization Reaction: Development and Mechanistic Studies.

Herein, we report the synthesis of 3-carbonyl-trisubstituted furans via Pd-catalyzed oxidative cycloisomerization reactions of 2-alkenyl-1,3-dicarbonyl scaffolds, using molecular oxygen as the sole oxidant to regenerate active palladium catalytic species, featuring good functional tolerance and mild reaction conditions. Deep investigation of intermediates and transition states of the reaction mechanism were conducted via experimental and DFT studies, providing a detailed mechanistical profile. The new developed methodology presents a greener alternative to Wacker-type cycloisomerizations and avoids the use of stoichiometric amounts of oxidants and strong acid additives.

Data relating to threats to passion fruit production in the Neotropics due to agricultural area loss and pollinator mismatch as consequence of climate changes.

The data in this article are associated with the research article 'Agricultural area losses and pollinator mismatch due to climate changes endanger passion fruit production in the Neotropics' (A.D. Bezerra et al. 2019). The data consists of the occurrence points, AUC scores models, presence and absence and co-occurrence maps of the passion fruit (Passiflora edulis) crop and its pollinators, Xylocopa bees (Xylocopa frontalis and Xylocopa grisescens), in current and future scenarios (RPC 4.5 and 8.5, in the years 2060 and 2080) in the Neotropics. Data was obtained though literature review (articles, systematic surveys, dissertation and thesis), as well as systematic searches in entomological collections available in data portals provided by the SpeciesLink and Global Biodiversity Information Facility - GIBF, and analyses by the MaxEnt algorithm and binary transformation. Occurrence error points that did not represent the actual spatial distribution of the species were removed to obtain the current occurrence points and data analyses proved good performance of models for all prediction scenarios. The data-generated maps of pollinators and crop occurrence and co-occurrence also show how climate change may impact the spatial distribution of pollinators and potential losses of this crop's agricultural areas.

Six-Step Syntheses of (-)-1-Deoxyaltronojirimycin and (+)-1-Deoxymannonojirimycin from N-Z-O-TBDPS-l-serinal.

Highly stereoselective six-step syntheses of (-)-1-deoxyaltronojirimycin (altro-DNJ) and (+)-1-deoxymannojirimycin (manno-DNJ) from N-Cbz-O-TBDPS-l-serinal are described. Key transformations involve a two-step preparation of a functionalized dihydropyridin-3-one as a common intermediate followed by Luche reduction and dihydroxylation (for altro-DNJ). The same sequence employing an epoxidation/epoxide opening in place of dihydroxylation furnishes manno-DNJ.

Three-step synthesis of (±)-preussin from decanal.

A straightforward and stereoselective synthesis of the alkaloid preussin is described starting from decanal and diethyl 3-diazo-2-oxopropylphosphonate. The key steps are an aza-Michael reaction from an α,ß-unsaturated diazoketone followed by a highly stereoselective Cu-catalyzed ylide formation and then a [1,2]-Stevens rearrangement. This strategy is feasible for extension to preussin analogues, demonstrating its utility for the rapid construction of all-cis-substituted pyrrolidines.

Synthesis of alkaloids: recent advances in the synthesis of phenanthroindolizidine alkaloids.

Phenanthroindolizidine alkaloids are a well-known class of compounds due to their interesting biological activities, especially anticancer ones. Represented by more than 60 substances, they are mainly isolated from plants of the Moraceae and Asclepiadaceae families. In the last 30 years, a great effort has been made aiming the synthesis of these compounds and analogues to be applied in medicinal chemistry.

Preparation of Z-α,ß-unsaturated diazoketones from aldehydes. Application in the construction of substituted dihydropyridin-3-ones.

The stereoselective preparation of α,ß-unsaturated diazoketones with Z geometry is described from aldehydes and a new olefination reagent. When prepared from amino aldehydes, these diazoketones could be converted to substituted dihydropyridin-3-ones in just one step, after an intramolecular N-H insertion reaction. The straightforward synthesis of a natural trihydroxylated piperidine demonstrates the utility of these unsaturated diazoketones for the rapid construction of piperidines.

Bioconversion of iodoacetophenones by marine fungi.

Nine marine fungi (Aspergillus sclerotiorum CBMAI 849, Aspergillus sydowii Ce19, Beauveria felina CBMAI 738, Mucor racemosus CBMAI 847, Penicillium citrinum CBMAI 1186, Penicillium miczynskii Ce16, P. miczynskii Gc5, Penicillium oxalicum CBMAI 1185, and Trichoderma sp. Gc1) catalyzed the asymmetric bioconversion of iodoacetophenones 1-3 to corresponding iodophenylethanols 6-8. All the marine fungi produced exclusively (S)-ortho-iodophenylethanol 6 and (S)-meta-iodophenylethanol 7 in accordance to the Prelog rule. B. felina CBMAI 738, P. miczynskii Gc5, P. oxalicum CBMAI 1185, and Trichoderma sp. Gc1 produced (R)-para-iodophenylethanol 8 as product anti-Prelog. The bioconversion of para-iodoacetophenone 3 with whole cells of P. oxalicum CBMAI 1185 showed competitive reduction-oxidation reactions.

Sintomatologia depressiva em pacientes alcoolatras internados

Existe uma vasta literatura que tenta estudar as variaveis relacionadas a uma possivel associacao entre alcoolismo e depressao. Neste trabalho, 18 paciente com o diagnostico de alcoolismo, internados num hospital psiquiatrico, foram avaliados em relacao a presenca de sintomatologia depressiva quatro e 28 dias apos a internacao. Eles tambem foram avaliados atraves de uma bateria de exames laboratoriais. Verificamos que a maioria dos pacientes melhorava da depressao com o correr da internacao, apesar de nenhum tratamento antidepressivo ter sido utilizado. Isto se acompanhava de uma tendencia de normalizacao dos resultados laboratoriais. Os resultados sao discutidos.

Psicobiologia dos disturbios afetivos

O grande desenvolvimento da neuroquimica nestas ultimas decadas tem possibilitado um grande avanco no estudo da psicobiologia dos disturbios afetivos, em geral, e das depressoes endogenas, em particular. Neste trabalho os autores apos conceituarem depressao endogena, diferenciando-a de depressao neurotica em relacao a sintomatologia, presenca de fatores precipitantes, tipode personalidade, padrao de sono, hereditariedade e resposta a tratamento, abordam as principais teorias psicobiologicas que foram desenvolvidas modernamente na tentativa de encontrar uma possivel etiologia para esta enfermidade. A teoria aminergica e particularizada, sendo discutidos alguns fatores ou achados que a confirmam ou desmentem. A importancia do fenomeno de 'kindling' e de possiveis disturbios de ritmos biologicos na producao da doenca afetiva tambem sao discutidas.