Adriano Baroni

Universidade Federal de Mato Grosso do Sul · Faculdade de Ciências Farmacêuticas, Alimentos e Nutrição

Rheumatoid arthritis (RA) is a chronic autoimmune disease that causes cartilage damage. Anti-inflammatories are widely used in the management of RA, but they can have side effects such as gastrointestinal and/or cardiovascular disorders. Studies published by our group showed that the synthesis of hybrid triazole analogs neolignan–celecoxib containi...

Neglected tropical diseases (NTDs) affect mainly poor and marginalized populations of tropical and subtropical areas in 150 countries. Many of the chemical processes involved in the synthesis of active pharmaceutical ingredients (APIs) are highly polluting and inefficient, both in terms of materials and energy-consuming. In this review, we present...

Chagas disease and leishmaniasis are neglected diseases of high priority as a public health problem. Pharmacotherapy is based on the administration of a few drugs, which exhibit hazardous adverse effects and toxicity to the patients. Thus, the search for new antitrypanosomatid drugs is imperative to overcome the limitations of the treatments. In th...

New treatment approaches targeting cutaneous leishmaniasis (CL) are required since conventional drugs exhibit limitations due to their several adverse effects and toxicity. In this study, we aimed to evaluate the in vivo intralesional treatment efficacy of five isoxazole derivatives previously synthesized and effective in vitro against intracellula...

Chagas disease (CD) is a neglected disease caused by the protozoan Trypanosoma cruzi. The two drugs used in the treatment schedules exhibit adverse effects and severe toxicity. Thus, searching for new antitrypanosomal agents is urgent to provide improved treatments to those affected by this disease. 5‐Nitrofuran‐isoxazole analogs were synthesized b...

Activated charcoal was prepared from Acrocomia aculeata (macaúba) endocarp by ZnCl2 activation and then used for the adsorptive purification of pretreated crude glycerol (CG) containing pigments, such as β-carotene. The pretreatment of glycerol involved filtration of the K3PO4 formed by the addition of H3PO4 to the crude glycerol containing KOH. A...

Essential oils are fat-soluble substances, however volatile comprising the secondary metabolism of plants. Since they are a mixture of various organic compounds, essential oils have extensive applicability in the pharmaceutical, cosmetic and food industries. Phenolic compounds such as anthocyanins and flavonoids are found in the Psidium cattleyanum...

This study reports the synthesis of novel neolignans-celecoxib hybrids and the evaluation of their biological activity. Analogs 8-13 (L13-L18) exhibited anti-inflammatory activity, inhibited glycoprotein expression (P-selectin) related to platelet activation, and were considered non- ulcerogenic in the animal model, even with the administration of...

SiO 2 -SO 3 H, with a surface area of 115 m ² /g, pore volumes of 0.38 cm ³ g ⁻¹ and 1.32 mmol H ⁺ /g, was used as a 10% w/w catalyst for the preparation of 5-hydroxymethyl-2-furfural (HMF) from fructose. A conversion of 100% was achieved in a microwave reactor during 10 min at 150 °C in DMSO, with 100% selectivity for HMF, at a molar ratio of fruc...

Chagas disease affects 6–8 million people worldwide, remaining a public health concern. Toxicity, several adverse effects and inefficiency in the chronic stage of the disease are the major challenges regarding the available treatment protocols. This work involved the synthesis of twenty‐two 1,4‐disubstituted‐1,2,3‐triazole analogues of benznidazole...

In this work, it is described the design of twenty-four heterocyclic amine-azachalcones compounds through molecular hybridization of chalcone scaffold and fragments of isoniazid, fluoroquinolones, and linezolid with antituberculosis potential. The new compounds were synthesized via Claisen-Schmidt condensation, providing yields of 36-95%. Fifteen c...

Natural products are viable sources for the design of new chemical entities that may have their activities improved by fast/inexpensive synthetic modifications of their substituents. Herein we report the synthesis of six analogs of 2,4,5-trimethoxybenzaldehyde (1), a phenolic derivate isolated from Duguetia furfuracea, their corresponding phytotoxi...

We developed and validated a stability-indicating assay method for the simultaneous determination of enrofloxacin and piroxicam in combination and in the presence of degradation products. Reverse-phase high-performance liquid chromatography analyses were carried out on a Vertisep C18 column and acetonitrile-water (48:52 v/v, pH 3.0) mobile phase wi...

In the search for new compounds with antileishmanial activity, we synthesized a triazole hybrid analogue of the neolignans grandisin and machilin G (LASQUIM 25), which was previously found highly active against both promastigotes and intracellular amastigote forms of Leishmania amazonensis. In this work, we investigated the leishmanicidal effects o...

Nineteen 3,5‐disubstituted‐isoxazole analogs were synthesized based on nitrofuran scaffolds, by a [3 + 2] cycloaddition reaction between terminal acetylenes and 5‐nitrofuran chloro‐oxime. The compounds were obtained in moderate to very good yields (45–91%). The antileishmanial activity was assayed against the promastigote and amastigote forms of Le...

Isoxazole analogues derived from the neolignans veraguensin, grandisin, and machilin G were previously synthesized with different substitution patterns through the bioisosterism strategy. These compounds were tested on intracellular amastigotes of Leishmania (Leishmania) amazonensis; the derivatives proved to be active against intracellular amastig...

A one‐pot protocol was developed for the synthesis of unsymmetrical 1,3‐butadiynes. The procedure is based on two sequential reactions: deprotection of R–C≡C–C≡C–C(Me)2OH derivatives in a retro‐Favorskii reaction to furnish a terminal 1,3‐butadiyne compound, which reacted with aryl iodides in a Sonogashira‐type cross‐coupling reaction catalyzed by...

Using bioisosterism as a medicinal chemistry tool, 16 3,5‐diaryl‐isoxazole analogues of the tetrahydrofuran neolignans veraguensin, grandisin and machilin G, were synthesized via 1,3‐dipolar cycloaddition reactions, with yields from 43–90%. Anti‐trypanosomatid activities were evaluated against Trypanosoma cruzi, Leishmania (L.) amazonensis and Leis...

This chapter aims to show the main applications of hydroalumination of alkenes and alkynes. The hydroalumination of terminal alkynes, symmetrical and asymmetrical internal alkynes, silyl acetylenes, tin acetylenes, as well as the preparation of (E) and (Z) vinyl organochalcogens are discussed in detail. The limitations of the hydroalumination of al...

We report herein the design and synthesis via click chemistry of twelve novel triazole retinoid analogues of tamibarotene (AM80) and the evaluation of their anticancer activities against six cancer cell lines: HL60, K562, 786, HT29, MCF7 and PC3. Among the synthesized compounds, two were more potent than tamibarotene against solid tumor cells, and...

Sixteen 1,4-diaryl-1,2,3-triazole compounds 4-19 derived from the tetrahydrofuran neolignans veraguensin 1, grandisin 2, and machilin G 3 were tested against Leishmania (Leishmania) amazonensis intracellular amastigotes. Triazole compounds 4-19 were synthetized via Click Chemistry strategy by 1,3-dipolar cycloaddition between terminal acetylenes an...

Sixteen 1,4-diaryl-1,2,3-triazole compounds derived from the natural products veraguensin, grandisin and machilin G were synthesized, with yields of 78-92%. Biological activity tests against Leishmania amazonensis promastigotes showed that three of these compounds were the most active, with maximum inhibitory concentration (IC 50) values of 1.1, 3....

A simple method for simultaneous determination of gatifloxacin and prednisolone acetate in ophthalmic formulation was developed and validated using UV spectrophotometry. Gatifloxacin and prednisolone acetate were quantified using the first-order derivative of the UV spectra. The proposed method was validated according to the guidelines of the Inter...

Biodiesel is obtained by transesterification of animal and vegetable triglycerides (fats), and have several advantages over fossil fuel, perhaps the most important being its renewable source and its lack of pollutants such as aromatic and sulfur components. However, biodiesel from vegetable sources such as Soya beans is expensive, and it raises the...

Various 3-iodothiophenes are synthesized in good to excellent yields and the formation of diiodobutadiene as by-product can be suppressed.

The aim of this study is to develop and validate a stability-indicating assay method for simultaneous determination of gatifloxacin and prednisolone acetate, or of ciprofloxacin hydrochloride and dexamethasone in combination and in the presence of degradation products. Reverse-phase high-performance liquid chromatography is used. All analyses were...

A simple synthesis of 3-iodothiophenes was demonstrated using a wide range of (Z)-thioenynes. The key step in the iodocyclofunctionalization was the selective reduction of the triple bond in (Z)-thioenynes by the addition of iodine as an electrophilic agent. The 3-iodothiophenes were obtained in good to excellent yields of 61–92%. The 3-iodothiophe...

Generally, the reactions using Bu4NOH are more rapid and efficient.

Hydrothiolation of symmetrical and unsymmetrical buta-1,3-diynes with sodium organylthiolate anions in reflux, generated in situ by reacting C4H9SH with NaOH, afforded (Z)-organylthioenynes in low to good yields (25–80%). By using tetrabutylammonium hydroxide (TBAOH) as base instead of NaOH, the hydrothiolation of buta-1,3-diynes was more rapid and...

An efficient and novel total synthesis of the two bioactive retinoids temarotene and arotinoid acid (TTNPB) is described. The key steps in this process include the regio and stereoselective hydrotelluration of thioacetylene 9 and Te/Li transmetalation of mixed (Z)-1,2-bis(organylchalcogene)-1-alkene (Z)-3. The subsequent reaction involving the β-ph...

Organic compounds containing the thiophenic structural unit are found in various synthetic compounds useful as agrochemicals, pharmaceuticals and liquid crystals. Because of the importance of these compounds in the area of medicinal chemistry was developed an efficient methodology for preparing 3-iodotiofenos via electrophilic cyclization of (Z)-th...

Retinoids are a class of natural and synthetic vitamin A analogues structurally related to all-trans-retinoic acid (ATRA). This class of compounds can inhibit cell proliferation and induce differentiation and apoptosis of cells, and several are used in cancer therapy. Using the concept of bioisosterism, new triazole analogues were designed from the...

Using the concept of bioisosterismo, the new analogs isoxazole were designed from the molecular modification of grandisin and veraguensin neolignans, which have a grouping that is a furan ring bioisóstero isoxazole. In order to obtain more potent compounds, and better physical and chemical characteristics, our research group synthesized six analogu...

Using the concept of bioisosterism, new triazole analogs were designed from the molecular modification of grandisin and veraguensin neolignans which have a furan group that is a bioisóstere of 1,2,3-triazoles ring. In order to obtain more potent compounds, with fewer side effects, and better physical and chemical characteristics in combating leishm...

Four- and eight-carbon homologation of benzaldehydes is described. The hydrotelluration of (Z)-1-methoxy-but-1-en-3-ynes 1 afforded (1Z,3Z)-1-butyltelluro-4-methoxy-1,3-butadiene 2, this compound 2 underwent a Te/Li exchange reaction, and the butadienyllithium 3 obtained reacted with benzaldehyde to form the corresponding allylic alcohol 4 with tot...

A novel one-pot synthesis of 1,1-dihalo-1-alkenes and 1,1-bis(butyltelluro)-1-alkenes was developed from hydrozirconation of alkynylzinc bromide with Cp2Zr(H)Cl and subsequent capture of the Zn/Zr 1,1-heterodimetallo-1-alkene intermediates with halogen and tellurium electrophiles. These protocols, which include multiple reactions in a one-pot proce...

Sequential treatment of silylacetylenes according to A)-C) allows a highly stereoselective synthesis of the title compounds (III) and (VII).

The products can be further converted into geminal enediynes such as (V).

The hydroalumination of silylacetylenes with DIBAL-H followed by the addition of n-butyllithium generated in situ the (Z)-β-vinylorganosilane alanates intermediates, which were trapped with butyltellurenyl bromide (C4H9TeBr), furnishing exclusively the (E)-1-butyltelluro-1-tri(organyl)silyl-2-organyl-1-alkenes in 45–70% yields. These telluro(silyl)...

Sonogashira cross-coupling reactions involving (E)-iodo vinyl stannanes and terminal acetylenes were carried out in the presence of Pd(PPh3)4, CuI and several amines, affording (Z)-tributylstannyl enynes in moderate to good yields (62–91%). Utilizing the catalytic system containing Pd(PPh3)4 (5%), CuI (10%), and TBAOH (40% in aqueous media) as acti...

The chemical variation of volatile constituents from leaves of Pimenta pseudocaryophyllus collected bimonthly for one year from a locality in the Atlantic Rain Forest, southeastern Brazil, was determined by GC/MS. Seven com- pounds were identified and characterized, revealing a predominance of phenylpropanoids (15.4–70.9%) and variable amounts of m...

One-pot hydrochalcogenation of 1-phenylthioacetylenes using organylselenolate and organyltellurolate anions generated by the insertions of selenium and tellurium in n-organyl lithium produced (Z)-1,2-bis(organylchalcogene)-1-alkenes. The chemical reactivity of these mixed 1,2-bis(organylchalcogene)-1-alkenes was studied by Te/Li and Se/Li stereoret...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Hydrodistillation of fresh leaves and rhizomes of Hedychium coronarium collected in the Atlantic rain forest of southeastern Brazil afforded essential oils in 0.68% and 0.20% yields, respectively. Analysis of the oils by GC and GC/MS revealed as predominant constituents in the leaf oil beta-caryophyllene (43.0%), caryophyllene oxide (12.1%) and bet...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Stannylacetylenes 7a−e react with Cp2Zr(H)Cl in THF at room temperature to give the α-zirconated vinylstannane intermediates 8a−e, which subsequently react with butyltellurenyl bromide (2.0 equiv) to give exclusively ketene stannyl(telluro) acetals 6a−e of E configuration. Similar reactions were performed using phenylselenenyl bromide (2.0 equiv) a...

Hydrodistillation of fresh leaves of Pimenta pseudocaryophyllus Gomes collected in the Atlantic Forest, south-eastern Brazil, afforded the essential oil in 0.48% yield. The major component was isolated from oil and analyzed by GC, GC/MS and NMR techniques, which revealed the compound chavibetol (70.9%). Others major constituents found were methyl e...

(1Z,3Z)-Butyltelluro-4-methoxy-1,3-butadiene 2 was obtained by the hydrotelluration of (Z)-1-methoxy-but-1-en-3-ynes 1. The butadienyllithium 3 obtained by the Te/Li exchange reaction in the (1Z,3Z)-1-butyltelluro-4-methoxy-1,3-butadiene 2 reacted with aldehydes to form the corresponding alcohols 4a–d with total retention of configuration. The alco...

A new, short total synthesis of dihydroactinidiolide 1 is described using selenium carbenium ion-promoted carbon–carbon bond formation as the key step. Our synthetic strategy starts with a lactonization reaction between 1,3,3-trimethylcyclohexene 13 and α-chloro-α-phenylseleno ethyl acetate 14, affording the key intermediate, α-phenylseleno-γ-butyr...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Dabdoub, Miguel J. Dabdoub, Vania B. Lenardao, Eder J. Hurtado, Gabriela R. Barbosa, Sandro L. Guerrero, Palimecio G., Jr. Nazario, Carlos E. D. Viana, Luiz H. Santana, Amanda S. Baroni, Adriano C. M.

Hydroalumination of thioacetylenes using DIBAL-H and lithium di-(isobutyl)-n-(butyl)-aluminate hydride (Zweifel's reagent), followed by addition of water, furnished exclusively the (Z)- and (E)-vinyl sulfides, respectively. The regio- and stereochemistry of the intermediates generated, (Z)- and (E)-phenylthio vinyl alanates, were determined by capt...

The hydroalumination of butylseleno acetylenes with DIBAL-H followed by addition of n-butyllithium generated in situ the (Z)-butylseleno vinyl alanates intermediates which were captured with C4H9TeBr furnishing the (E)-telluro(seleno)ketene acetals exclusively. The isomers with opposite stereochemistry (Z)-telluro(seleno)ketene acetals were obtaine...

A clean, efficient and fast method for esterification reactions for sterically (biodiesels) or otherwise inactive (aromatic) precursors was developed, using catalysts supported in a solid phase under “solvent free” conditions, and whose reactions can be promoted by MW irradiation.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

The hydroselenation of 1-organyl-1,3-butadiynes and 1,4-diorganyl-1,3-butadiynes with the sodium phenylselenolate anion, which was generated in situ by reacting diphenyl diselenide with NaBH4 in aqueous ethanol, results in the regio-, stereo- and chemoselective formation the 1-phenylseleno-4-organyl-1-buten-3-ynes and 1-phenylseleno-1, 1-diorganyl-...

Stannylacetylenes 7a-e react with Cp(2)Zr(H)Cl in THF at room temperature to give the alpha-zirconated vinylstannane intermediates 8a-e, which subsequently react with butyltellurenyl bromide (2.0 equiv) to give exclusively ketene stannyl(telluro) acetals 6a-e of E configuration. Similar reactions were performed using phenylselenenyl bromide (2.0 eq...

Lithium alkynylselenolate anions react completely with 1.0 equiv of Cp(2)Zr(H)Cl in THF at room temperature to give exclusively the alpha-zirconated vinylselenolate intermediates 23-27, which by treatment with an alkyl halide afforded the alpha-zirconated vinyl alkylselenide intermediates 29-33. Reaction of 29-33 with butyltellurenyl bromide result...

Lithium alkynylselenolate anions react completely with 1.0 equiv of Cp2Zr(H)Cl in THF at room temperature to give exclusively the α-zirconated vinylselenolate intermediates 23−27, which by treatment with an alkyl halide afforded the α-zirconated vinyl alkylselenide intermediates 29−33. Reaction of 29−33 with butyltellurenyl bromide results in the f...