Mariola Zielinska-Błajet - Academia.edu (original) (raw)

Papers by Mariola Zielinska-Błajet

An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The Royal Society of Chemistry eBooks, Dec 16, 2016

Arkivoc, Nov 18, 2022

A mini-review presents advances in the application of graphene-based materials in catalytic stere... more A mini-review presents advances in the application of graphene-based materials in catalytic stereoselective synthesis. Examples of chiral organocatalysts and metal complexes immobilized on carbon nanosheets are discussed.

Tetrahedron, May 1, 2005

A new and convenient method for the stereospecific synthesis of variously substituted 1,3-oxazoli... more A new and convenient method for the stereospecific synthesis of variously substituted 1,3-oxazolidin-2-ones from the easily available b-hydroxyalkyl phenyl selenides is presented. After transformation into the N-tosyl or N-benzoyl carbamates, the selenides were oxidized to the corresponding selenones. The key step of the process is the ring-closure reaction, which occurs by stereospecific intramolecular nucleophilic substitution of the selenone group by the nitrogen atom of the carbamate. Enantiomerically pure 1,3-oxazolidin-2-one derivatives can be easily prepared by using enantiomerically pure b-hydroxyalkyl phenyl selenides as starting materials.

The Alkaloids: Chemistry and Biology, 2019

Major Cinchona alkaloids quinine, quinidine, cinchonine, and cinchonidine are available chiral na... more Major Cinchona alkaloids quinine, quinidine, cinchonine, and cinchonidine are available chiral natural compounds (chiral pool). Unlike many other natural products, these alkaloids are available in multiple diastereomeric forms which are separated on an industrial scale. The introduction discusses in short conformational equilibria, traditional separation scheme, biosynthesis, and de novo chemical syntheses. The second section concerns useful chemical applications of the alkaloids as chiral recognition agents and effective chiral catalysts. Besides the Sharpless ethers and quaternary ammonium salts (chiral PTC), the most successful bifunctional organocatalysts are based on 9-amino derivatives: thioureas and squaramides. The third section reports the main transformations of Cinchona alkaloids. This covers reactions of the 9-hydroxyl group with the retention or inversion of configuration. Specific Cinchona rearrangements enlarging [2.2.2]bicycle of quinuclidine to [3.2.2] products are connected to the 9-OH substitution. The syntheses of numerous esterification and etherification products are described, including many examples of bi-Cinchona alkaloid ethers. Further derivatives comprise 9-N-substituted compounds. The amino group is introduced via an azido function with the inversion of configuration at the stereogenic center C9. The 9-epi-amino-alkaloids provide imines, amides, imides, thioureas, and squaramides. The syntheses of 9-carbon-, 9-sulfur-, and 9-selenium-substituted derivatives are discussed. Oxidation of the hydroxyl group of any alkaloid gives ketones, which can be selectively reduced, reacted with Grignard reagents, or subjected to the Corey-Chaykovsky reaction. The alkaloids were also partially degraded by splitting C4'-C9 or N1-C8 bonds. In order to immobilize Cinchona alkaloids the transformations of the 3-vinyl group were often exploited. Finally, miscellaneous functionalizations of quinuclidine, quinoline, and examples of various metal complexes of the alkaloids are considered.

Tetrahedron-asymmetry, Feb 1, 2011

A complex derived from the enantiomeric bipiperidine and copper(II) acetate hydrate is an efficie... more A complex derived from the enantiomeric bipiperidine and copper(II) acetate hydrate is an efficient catalyst for the enantioselective Henry reaction. The easy availability of both catalyst components, mild reaction conditions, high yield, and good to excellent enantioselectivity make the catalyst useful for everyday practice.

ChemInform, May 23, 2010

Objective: Oxime is an important precursor for many reactions like Beckmann rearrangement, oxime ... more Objective: Oxime is an important precursor for many reactions like Beckmann rearrangement, oxime ether preparation etc. Oxime is generally prepared in strong acidic [1], strong basic [2] medium. Even some methods involving mild basic medium [3] is also known. But these procedures involve hazardous chemicals like inorganic acid, inorganic base, organic bases like Pyridine [4], Hy amine [5] etc. Some green methodologies have been also developed but that also involves expensive reagents like Bi2O3 [6] etc. In this context, this work has been carried out to develop a new methodology for oxime preparation. Methods: Different oxims have been prepared in heating condition using water-ethanol medium and alumina as a base. Products have been isolated by column chromatography using 200 mesh silica gel followed by fractional crystallization. Products were verified by melting point analysis. Results: Four different aromatic oxims have been prepared in excellent yield and in an economically viable condition. Conclusion: Here preparation of oxime in a mild basic medium has been reported. Alumina (Al2O3) is pretty cheap and not mentionable hazardous and it has been used here for the first time in synthesis of oxime.

ChemPlusChem, 2020

The anion binding ability of a family of bis‐selenoureas L1‐L3 obtained by the reaction of 1,3‐bi... more The anion binding ability of a family of bis‐selenoureas L1‐L3 obtained by the reaction of 1,3‐bis(aminomethyl)‐benzene and phenylisoselenocyanate, p‐methoxyphenylisoselenocyanate and naphtylisoselenocyanate, for L1, L2, and L3, respectively, has been tested and compared to that of previously described bis‐urea analogues. Results suggest that the introduction of selenium leads to an increase in the acidity of the urea NH hydrogen atoms, and therefore to a stronger affinity (more than three‐fold higher) towards anion species, in particular dihydrogen phosphate, in DMSO‐d6. Theoretical calculations allowed for the optimization of the adducts receptors corroborating the experimental results.

An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Comprehensive Organic Chemistry Experiments for the Laboratory Classroom

This expansive and practical textbook contains organic chemistry experiments for teaching in the ... more This expansive and practical textbook contains organic chemistry experiments for teaching in the laboratory at the undergraduate level covering a range of functional group transformations and key organic reactions.The editorial team have collected contributions from around the world and standardized them for publication. Each experiment will explore a modern chemistry scenario, such as: sustainable chemistry; application in the pharmaceutical industry; catalysis and material sciences, to name a few. All the experiments will be complemented with a set of questions to challenge the students and a section for the instructors, concerning the results obtained and advice on getting the best outcome from the experiment. A section covering practical aspects with tips and advice for the instructors, together with the results obtained in the laboratory by students, has been compiled for each experiment. Targeted at professors and lecturers in chemistry, this useful text will provide up to dat...

Molecules, 2021

By varying the steric and electronic surroundings of the hydrogen-bonding motif, the novel chiral... more By varying the steric and electronic surroundings of the hydrogen-bonding motif, the novel chiral Cinchona-alkaloid based selenoureas were developed. Acting as bifunctional catalysts, they were applied in the Michael reactions of dithiomalonate and nitrostyrene providing chiral adducts with up to 96% ee. The asymmetric Michael–-hemiacetalization reaction of benzylidene pyruvate and dimedone, performed with the assistance of 5 mol% of selenoureas, furnished the product with up to 93% ee and excellent yields. The effectiveness of the new hydrogen-bond donors was also proved in solvent-free reactions under ball mill conditions, supporting the sustainability of the devised catalytic protocol.

Materials, 2021

An efficient approach to the synthesis of chiral selenoureas consisting of Cinchona alkaloid scaf... more An efficient approach to the synthesis of chiral selenoureas consisting of Cinchona alkaloid scaffolds was described. The new selenoureas were assessed as bifunctional organocatalysts in the asymmetric Michael addition reactions under mild conditions. The best results were obtained for selenoureas bearing the 4-fluorophenyl group. These catalysts promoted the reactions with enantioselectivities of up to 96% ee. Additionally, the catalytic performance of the thiourea and selenourea counterpart was compared.

International Journal of Molecular Sciences, 2020

Monoterpenes, comprising hydrocarbons, are the largest class of plant secondary metabolites and a... more Monoterpenes, comprising hydrocarbons, are the largest class of plant secondary metabolites and are commonly found in essential oils. Monoterpenes and their derivatives are key ingredients in the design and production of new biologically active compounds. This review focuses on selected aliphatic, monocyclic, and bicyclic monoterpenes like geraniol, thymol, myrtenal, pinene, camphor, borneol, and their modified structures. The compounds in question play a pivotal role in biological and medical applications. The review also discusses anti-inflammatory, antimicrobial, anticonvulsant, analgesic, antiviral, anticancer, antituberculosis, and antioxidant biological activities exhibited by monoterpenes and their derivatives. Particular attention is paid to the link between biological activity and the effect of structural modification of monoterpenes and monoterpenoids, as well as the introduction of various functionalized moieties into the molecules in question.

Symmetry, 2021

A series of new bidentate N,S-ligands—aziridines containing a para-substituted phenyl sulfide gro... more A series of new bidentate N,S-ligands—aziridines containing a para-substituted phenyl sulfide group—was synthesized and evaluated in the Pd-catalyzed Tsuji–Trost reaction and addition of diethylzinc and phenylethynylzinc to benzaldehyde. A high enantiomeric ratio for the addition reactions (up to 94.2:5.8) was obtained using the aziridine ligand bearing a p-nitro phenyl sulfide group. Collected results reveal a specific electronic effect that, by the presence of particular electron-donating or electron-withdrawing groups in the PhS- moiety, influences the σ-donor–metal binding and the enantioselectivity of the catalyzed reactions.

International Journal of Molecular Sciences, 2021

Terpenes—a diverse group of secondary metabolites—constitute the largest class of natural product... more Terpenes—a diverse group of secondary metabolites—constitute the largest class of natural products abundant in almost every plant species. The properties of concrete terpenes and essential oils have been intensively studied due to their widespread use in the pharmaceutical, food and cosmetics industries. Despite the popularity of these aromatic compounds, their derivatives, terpenoids, are still not comprehensively characterized despite exhibiting potent bioactive properties. This review aims to assess the anticancer properties of selected monoterpenes including carvone, carvacrol, perillyl alcohol, perillaldehyde, limonene, menthol and their derivatives while also evaluating potential applications as novel anticancer treatments. Special attention is paid to functional groups that improve the bioactivity of monoterpene molecules. This review also covers the therapeutic potential of deep eutectic solvents that contain monoterpene substances. Taken together, the literature supports th...

Tetrahedron-asymmetry, 2011

A highly enantioselective Henry reaction has been developed using a chiral copper(II)– gluco BOX ... more A highly enantioselective Henry reaction has been developed using a chiral copper(II)– gluco BOX complex. The catalytic system works well with a wide range of aromatic, aliphatic and heteroaromatic aldehydes to afford the corresponding nitroalkanols with high enantioselectivity (up to 99%) in excellent yields (up to 95%). The catalyst shows good enantioselectivity with 10 mol % of loading at easily attainable temperature (10 °C) even in the absence of an inert atmosphere.

Chemistry - A European Journal, 2004

A new and convenient method for the stereospecific synthesis of variously substituted 1,3-oxazoli... more A new and convenient method for the stereospecific synthesis of variously substituted 1,3-oxazolidin-2-ones from the easily available b-hydroxyalkyl phenyl selenides is presented. After transformation into the N-tosyl or N-benzoyl carbamates, the selenides were oxidized to the corresponding selenones. The key step of the process is the ring-closure reaction, which occurs by stereospecific intramolecular nucleophilic substitution of the selenone group by the nitrogen atom of the carbamate. Enantiomerically pure 1,3-oxazolidin-2-one derivatives can be easily prepared by using enantiomerically pure b-hydroxyalkyl phenyl selenides as starting materials.

Tetrahedron Asymmetry, 2002

Readily available (+)-(R)-1,3-diphenyl-3-phenylsulfanyl-propan-1-one 1 was oxidized to the corres... more Readily available (+)-(R)-1,3-diphenyl-3-phenylsulfanyl-propan-1-one 1 was oxidized to the corresponding sulfone and its reduction gave separable (1R,3R)- and (1S,3R)-1,3-diphenyl-3-phenylsulfonylpropan-1-ols. When 1 was reduced to the mixture of epimeric alcohols, subsequent reaction with three different sulfoxidation agents allowed the separation of all four diastereomeric 1,3-diphenyl-3-phenylsulfinylpropan-1-ols in diastereomerically pure form. The absolute configuration at the newly created stereogenic carbon was proved by chemical correlation, while the configuration of the sulfur centre of the phenylsulfinyl group was established by CD spectroscopy.Sequential reduction and oxidation allow for the preparation of the title compounds with all possible configurations at the newly created stereogenic centers. Chemical correlation and CD spectroscopic analysis proved the configuration of the products. The obtained chiral derivatives were further transformed in several ways documenting their synthetic utility.(+)-(1R,3R)-1,3-Diphenyl-3-phenylsulfonylpropan-1-olC21H20O3SEe >95%De=100% (determined by 1H NMR)[α]D +59 (0.96, CH2Cl2)Source of chirality: diastereoselective reduction of (R)-1,3-diphenyl-3-phenylsulfonylpropan-1-one and recrystallizationAbsolute configuration: 1R,3R (determined by chemical correlation)(+)-(1S,3R)-(1,3-Diphenyl-3-phenylsulfonylpropyl) methanesulfonateC22H22O5S2Ee >95%De=100% (determined by 1H NMR)[α]D +50 (0.51, CH2Cl2)Source of chirality: esterification of (1S,3R)-1,3-diphenyl-3-phenylsulfonylpropan-1-olAbsolute configuration: 1S,3R (determined by chemical correlation)(−)-(1R,2R)-1,2-Diphenyl-1-phenylsulfonylcyclopropaneC21H18O2SEe >95%De=100% (determined by 1H NMR)[α]D −141 (0.6, CH2Cl2)Source of chirality: intramolecular SN2 reaction of (1S,3R)-(1,3-diphenyl-3-phenylsulfonylpropyl) methanesulfonateAbsolute configuration: 1R,2R (determined by chemical correlation and 2D NMR measurement)(+)-(1S,3R,RS)-1,3-Diphenyl-3-phenylsulfinylpropan-1-olC21H20O2SEe >95%De=100% (determined by 1H NMR)[α]D +53 (0.2, CH2Cl2)Source of chirality: diastereoselective sulfoxidation and recrystallizationAbsolute configuration: 1S,3R,RS (determined by chemical correlation and CD measurement)(+)-(1S,3R,SS)-1,3-Diphenyl-3-phenylsulfinylpropan-1-olC21H20O2SEe >95%De=100% (determined by 1H NMR)[α]D +65 (0.75, CH2Cl2)Source of chirality: diastereoselective sulfoxidation and recrystallizationAbsolute configuration: 1S,3R,SS (determined by chemical correlation and CD measurement)(+)-(1R,3R,SS)-1,3-Diphenyl-3-phenylsulfinylpropan-1-olC21H20O2SEe >95%De=100% (determined by 1H NMR)[α]D +97 (0.6, CH2Cl2)Source of chirality: diastereoselective sulfoxidation and recrystallizationAbsolute configuration: 1R,3R,SS (determined by chemical correlation and CD measurement)(+)-(1R,3R,RS)-1,3-Diphenyl-3-phenylsulfinylpropan-1-olC21H20O2SEe >95%De=100% (determined by 1H NMR)[α]D +126 (0.7, CH2Cl2)Source of chirality: diastereoselective sulfoxidation and recrystallizationAbsolute configuration: 1R,3R,RS (determined by chemical correlation and CD measurement)

An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The Royal Society of Chemistry eBooks, Dec 16, 2016

Arkivoc, Nov 18, 2022

A mini-review presents advances in the application of graphene-based materials in catalytic stere... more A mini-review presents advances in the application of graphene-based materials in catalytic stereoselective synthesis. Examples of chiral organocatalysts and metal complexes immobilized on carbon nanosheets are discussed.

Tetrahedron, May 1, 2005

A new and convenient method for the stereospecific synthesis of variously substituted 1,3-oxazoli... more A new and convenient method for the stereospecific synthesis of variously substituted 1,3-oxazolidin-2-ones from the easily available b-hydroxyalkyl phenyl selenides is presented. After transformation into the N-tosyl or N-benzoyl carbamates, the selenides were oxidized to the corresponding selenones. The key step of the process is the ring-closure reaction, which occurs by stereospecific intramolecular nucleophilic substitution of the selenone group by the nitrogen atom of the carbamate. Enantiomerically pure 1,3-oxazolidin-2-one derivatives can be easily prepared by using enantiomerically pure b-hydroxyalkyl phenyl selenides as starting materials.

The Alkaloids: Chemistry and Biology, 2019

Major Cinchona alkaloids quinine, quinidine, cinchonine, and cinchonidine are available chiral na... more Major Cinchona alkaloids quinine, quinidine, cinchonine, and cinchonidine are available chiral natural compounds (chiral pool). Unlike many other natural products, these alkaloids are available in multiple diastereomeric forms which are separated on an industrial scale. The introduction discusses in short conformational equilibria, traditional separation scheme, biosynthesis, and de novo chemical syntheses. The second section concerns useful chemical applications of the alkaloids as chiral recognition agents and effective chiral catalysts. Besides the Sharpless ethers and quaternary ammonium salts (chiral PTC), the most successful bifunctional organocatalysts are based on 9-amino derivatives: thioureas and squaramides. The third section reports the main transformations of Cinchona alkaloids. This covers reactions of the 9-hydroxyl group with the retention or inversion of configuration. Specific Cinchona rearrangements enlarging [2.2.2]bicycle of quinuclidine to [3.2.2] products are connected to the 9-OH substitution. The syntheses of numerous esterification and etherification products are described, including many examples of bi-Cinchona alkaloid ethers. Further derivatives comprise 9-N-substituted compounds. The amino group is introduced via an azido function with the inversion of configuration at the stereogenic center C9. The 9-epi-amino-alkaloids provide imines, amides, imides, thioureas, and squaramides. The syntheses of 9-carbon-, 9-sulfur-, and 9-selenium-substituted derivatives are discussed. Oxidation of the hydroxyl group of any alkaloid gives ketones, which can be selectively reduced, reacted with Grignard reagents, or subjected to the Corey-Chaykovsky reaction. The alkaloids were also partially degraded by splitting C4'-C9 or N1-C8 bonds. In order to immobilize Cinchona alkaloids the transformations of the 3-vinyl group were often exploited. Finally, miscellaneous functionalizations of quinuclidine, quinoline, and examples of various metal complexes of the alkaloids are considered.

Tetrahedron-asymmetry, Feb 1, 2011

A complex derived from the enantiomeric bipiperidine and copper(II) acetate hydrate is an efficie... more A complex derived from the enantiomeric bipiperidine and copper(II) acetate hydrate is an efficient catalyst for the enantioselective Henry reaction. The easy availability of both catalyst components, mild reaction conditions, high yield, and good to excellent enantioselectivity make the catalyst useful for everyday practice.

ChemInform, May 23, 2010

Objective: Oxime is an important precursor for many reactions like Beckmann rearrangement, oxime ... more Objective: Oxime is an important precursor for many reactions like Beckmann rearrangement, oxime ether preparation etc. Oxime is generally prepared in strong acidic [1], strong basic [2] medium. Even some methods involving mild basic medium [3] is also known. But these procedures involve hazardous chemicals like inorganic acid, inorganic base, organic bases like Pyridine [4], Hy amine [5] etc. Some green methodologies have been also developed but that also involves expensive reagents like Bi2O3 [6] etc. In this context, this work has been carried out to develop a new methodology for oxime preparation. Methods: Different oxims have been prepared in heating condition using water-ethanol medium and alumina as a base. Products have been isolated by column chromatography using 200 mesh silica gel followed by fractional crystallization. Products were verified by melting point analysis. Results: Four different aromatic oxims have been prepared in excellent yield and in an economically viable condition. Conclusion: Here preparation of oxime in a mild basic medium has been reported. Alumina (Al2O3) is pretty cheap and not mentionable hazardous and it has been used here for the first time in synthesis of oxime.

ChemPlusChem, 2020

The anion binding ability of a family of bis‐selenoureas L1‐L3 obtained by the reaction of 1,3‐bi... more The anion binding ability of a family of bis‐selenoureas L1‐L3 obtained by the reaction of 1,3‐bis(aminomethyl)‐benzene and phenylisoselenocyanate, p‐methoxyphenylisoselenocyanate and naphtylisoselenocyanate, for L1, L2, and L3, respectively, has been tested and compared to that of previously described bis‐urea analogues. Results suggest that the introduction of selenium leads to an increase in the acidity of the urea NH hydrogen atoms, and therefore to a stronger affinity (more than three‐fold higher) towards anion species, in particular dihydrogen phosphate, in DMSO‐d6. Theoretical calculations allowed for the optimization of the adducts receptors corroborating the experimental results.

An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Comprehensive Organic Chemistry Experiments for the Laboratory Classroom

This expansive and practical textbook contains organic chemistry experiments for teaching in the ... more This expansive and practical textbook contains organic chemistry experiments for teaching in the laboratory at the undergraduate level covering a range of functional group transformations and key organic reactions.The editorial team have collected contributions from around the world and standardized them for publication. Each experiment will explore a modern chemistry scenario, such as: sustainable chemistry; application in the pharmaceutical industry; catalysis and material sciences, to name a few. All the experiments will be complemented with a set of questions to challenge the students and a section for the instructors, concerning the results obtained and advice on getting the best outcome from the experiment. A section covering practical aspects with tips and advice for the instructors, together with the results obtained in the laboratory by students, has been compiled for each experiment. Targeted at professors and lecturers in chemistry, this useful text will provide up to dat...

Molecules, 2021

By varying the steric and electronic surroundings of the hydrogen-bonding motif, the novel chiral... more By varying the steric and electronic surroundings of the hydrogen-bonding motif, the novel chiral Cinchona-alkaloid based selenoureas were developed. Acting as bifunctional catalysts, they were applied in the Michael reactions of dithiomalonate and nitrostyrene providing chiral adducts with up to 96% ee. The asymmetric Michael–-hemiacetalization reaction of benzylidene pyruvate and dimedone, performed with the assistance of 5 mol% of selenoureas, furnished the product with up to 93% ee and excellent yields. The effectiveness of the new hydrogen-bond donors was also proved in solvent-free reactions under ball mill conditions, supporting the sustainability of the devised catalytic protocol.

Materials, 2021

An efficient approach to the synthesis of chiral selenoureas consisting of Cinchona alkaloid scaf... more An efficient approach to the synthesis of chiral selenoureas consisting of Cinchona alkaloid scaffolds was described. The new selenoureas were assessed as bifunctional organocatalysts in the asymmetric Michael addition reactions under mild conditions. The best results were obtained for selenoureas bearing the 4-fluorophenyl group. These catalysts promoted the reactions with enantioselectivities of up to 96% ee. Additionally, the catalytic performance of the thiourea and selenourea counterpart was compared.

International Journal of Molecular Sciences, 2020

Monoterpenes, comprising hydrocarbons, are the largest class of plant secondary metabolites and a... more Monoterpenes, comprising hydrocarbons, are the largest class of plant secondary metabolites and are commonly found in essential oils. Monoterpenes and their derivatives are key ingredients in the design and production of new biologically active compounds. This review focuses on selected aliphatic, monocyclic, and bicyclic monoterpenes like geraniol, thymol, myrtenal, pinene, camphor, borneol, and their modified structures. The compounds in question play a pivotal role in biological and medical applications. The review also discusses anti-inflammatory, antimicrobial, anticonvulsant, analgesic, antiviral, anticancer, antituberculosis, and antioxidant biological activities exhibited by monoterpenes and their derivatives. Particular attention is paid to the link between biological activity and the effect of structural modification of monoterpenes and monoterpenoids, as well as the introduction of various functionalized moieties into the molecules in question.

Symmetry, 2021

A series of new bidentate N,S-ligands—aziridines containing a para-substituted phenyl sulfide gro... more A series of new bidentate N,S-ligands—aziridines containing a para-substituted phenyl sulfide group—was synthesized and evaluated in the Pd-catalyzed Tsuji–Trost reaction and addition of diethylzinc and phenylethynylzinc to benzaldehyde. A high enantiomeric ratio for the addition reactions (up to 94.2:5.8) was obtained using the aziridine ligand bearing a p-nitro phenyl sulfide group. Collected results reveal a specific electronic effect that, by the presence of particular electron-donating or electron-withdrawing groups in the PhS- moiety, influences the σ-donor–metal binding and the enantioselectivity of the catalyzed reactions.

International Journal of Molecular Sciences, 2021

Terpenes—a diverse group of secondary metabolites—constitute the largest class of natural product... more Terpenes—a diverse group of secondary metabolites—constitute the largest class of natural products abundant in almost every plant species. The properties of concrete terpenes and essential oils have been intensively studied due to their widespread use in the pharmaceutical, food and cosmetics industries. Despite the popularity of these aromatic compounds, their derivatives, terpenoids, are still not comprehensively characterized despite exhibiting potent bioactive properties. This review aims to assess the anticancer properties of selected monoterpenes including carvone, carvacrol, perillyl alcohol, perillaldehyde, limonene, menthol and their derivatives while also evaluating potential applications as novel anticancer treatments. Special attention is paid to functional groups that improve the bioactivity of monoterpene molecules. This review also covers the therapeutic potential of deep eutectic solvents that contain monoterpene substances. Taken together, the literature supports th...

Tetrahedron-asymmetry, 2011

A highly enantioselective Henry reaction has been developed using a chiral copper(II)– gluco BOX ... more A highly enantioselective Henry reaction has been developed using a chiral copper(II)– gluco BOX complex. The catalytic system works well with a wide range of aromatic, aliphatic and heteroaromatic aldehydes to afford the corresponding nitroalkanols with high enantioselectivity (up to 99%) in excellent yields (up to 95%). The catalyst shows good enantioselectivity with 10 mol % of loading at easily attainable temperature (10 °C) even in the absence of an inert atmosphere.

Chemistry - A European Journal, 2004

A new and convenient method for the stereospecific synthesis of variously substituted 1,3-oxazoli... more A new and convenient method for the stereospecific synthesis of variously substituted 1,3-oxazolidin-2-ones from the easily available b-hydroxyalkyl phenyl selenides is presented. After transformation into the N-tosyl or N-benzoyl carbamates, the selenides were oxidized to the corresponding selenones. The key step of the process is the ring-closure reaction, which occurs by stereospecific intramolecular nucleophilic substitution of the selenone group by the nitrogen atom of the carbamate. Enantiomerically pure 1,3-oxazolidin-2-one derivatives can be easily prepared by using enantiomerically pure b-hydroxyalkyl phenyl selenides as starting materials.

Tetrahedron Asymmetry, 2002

Readily available (+)-(R)-1,3-diphenyl-3-phenylsulfanyl-propan-1-one 1 was oxidized to the corres... more Readily available (+)-(R)-1,3-diphenyl-3-phenylsulfanyl-propan-1-one 1 was oxidized to the corresponding sulfone and its reduction gave separable (1R,3R)- and (1S,3R)-1,3-diphenyl-3-phenylsulfonylpropan-1-ols. When 1 was reduced to the mixture of epimeric alcohols, subsequent reaction with three different sulfoxidation agents allowed the separation of all four diastereomeric 1,3-diphenyl-3-phenylsulfinylpropan-1-ols in diastereomerically pure form. The absolute configuration at the newly created stereogenic carbon was proved by chemical correlation, while the configuration of the sulfur centre of the phenylsulfinyl group was established by CD spectroscopy.Sequential reduction and oxidation allow for the preparation of the title compounds with all possible configurations at the newly created stereogenic centers. Chemical correlation and CD spectroscopic analysis proved the configuration of the products. The obtained chiral derivatives were further transformed in several ways documenting their synthetic utility.(+)-(1R,3R)-1,3-Diphenyl-3-phenylsulfonylpropan-1-olC21H20O3SEe >95%De=100% (determined by 1H NMR)[α]D +59 (0.96, CH2Cl2)Source of chirality: diastereoselective reduction of (R)-1,3-diphenyl-3-phenylsulfonylpropan-1-one and recrystallizationAbsolute configuration: 1R,3R (determined by chemical correlation)(+)-(1S,3R)-(1,3-Diphenyl-3-phenylsulfonylpropyl) methanesulfonateC22H22O5S2Ee >95%De=100% (determined by 1H NMR)[α]D +50 (0.51, CH2Cl2)Source of chirality: esterification of (1S,3R)-1,3-diphenyl-3-phenylsulfonylpropan-1-olAbsolute configuration: 1S,3R (determined by chemical correlation)(−)-(1R,2R)-1,2-Diphenyl-1-phenylsulfonylcyclopropaneC21H18O2SEe >95%De=100% (determined by 1H NMR)[α]D −141 (0.6, CH2Cl2)Source of chirality: intramolecular SN2 reaction of (1S,3R)-(1,3-diphenyl-3-phenylsulfonylpropyl) methanesulfonateAbsolute configuration: 1R,2R (determined by chemical correlation and 2D NMR measurement)(+)-(1S,3R,RS)-1,3-Diphenyl-3-phenylsulfinylpropan-1-olC21H20O2SEe >95%De=100% (determined by 1H NMR)[α]D +53 (0.2, CH2Cl2)Source of chirality: diastereoselective sulfoxidation and recrystallizationAbsolute configuration: 1S,3R,RS (determined by chemical correlation and CD measurement)(+)-(1S,3R,SS)-1,3-Diphenyl-3-phenylsulfinylpropan-1-olC21H20O2SEe >95%De=100% (determined by 1H NMR)[α]D +65 (0.75, CH2Cl2)Source of chirality: diastereoselective sulfoxidation and recrystallizationAbsolute configuration: 1S,3R,SS (determined by chemical correlation and CD measurement)(+)-(1R,3R,SS)-1,3-Diphenyl-3-phenylsulfinylpropan-1-olC21H20O2SEe >95%De=100% (determined by 1H NMR)[α]D +97 (0.6, CH2Cl2)Source of chirality: diastereoselective sulfoxidation and recrystallizationAbsolute configuration: 1R,3R,SS (determined by chemical correlation and CD measurement)(+)-(1R,3R,RS)-1,3-Diphenyl-3-phenylsulfinylpropan-1-olC21H20O2SEe >95%De=100% (determined by 1H NMR)[α]D +126 (0.7, CH2Cl2)Source of chirality: diastereoselective sulfoxidation and recrystallizationAbsolute configuration: 1R,3R,RS (determined by chemical correlation and CD measurement)