Dariusz Deredas - Academia.edu (original) (raw)
Papers by Dariusz Deredas
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.
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.
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.
Chemical Communications, 2008
Carbohydrate Research, 1994
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.
Tetrahedron, 2003
Carbohydrates Carbohydrates U 0500 Stereocontrolled Synthesis of Imidazolo[1,5]hexopiperidinoses ... more Carbohydrates Carbohydrates U 0500 Stereocontrolled Synthesis of Imidazolo[1,5]hexopiperidinoses and Imidazol-4(5)-yl-C-glycosides.-The synthesis of five imidazolohexopiperidinoses and three imidazolyl-C-glycosides is presented, involving an SN2-type cyclization of suitably substituted imidazolylpentitols. The reaction outcome is strongly influenced by steric requirements. Thus, imidazolohexopiperidinoses (VI), (X) and (XII) are readily formed in the L-galacto, D-ido, D-gulo and D-manno series, while their formation is suppressed in the L-talo and D-gluco series and imidazolyl-C-glycosides (VIII), (XV) and (XVI) are obtained instead.
Tetrahedron, 2007
ABSTRACT A new route for the synthesis of imidazolosugars—6-deoxyimidazolopiperidinoses 1 and 2 a... more ABSTRACT A new route for the synthesis of imidazolosugars—6-deoxyimidazolopiperidinoses 1 and 2 and 7-deoxyimidazoloazepanoses 3 and 4 in two enantiomerical forms—is reported. The new synthetic approach is based on two key reactions: (i) stereocontrolled Wittig Z-olefination of an imidazolecarbaldehyde with phosphoranes containing one chiral centre, obtained from (S)- and (R)-1,2,4-butantriol; (ii) diastereoselective cis-dihydroxylation of previously obtained olefins. All synthesised imidazolosugars were evaluated as potential inhibitors of glycosidases.
Tetrahedron, 1998
ABSTRACT Imidazolo-L-lyxo-piperidinose 4 was synthesised from the D-galactose derivative 8 by two... more ABSTRACT Imidazolo-L-lyxo-piperidinose 4 was synthesised from the D-galactose derivative 8 by two reaction sequences, via removal of a terminal carbon atom, stepwise incorporation of an imidazole moiety, and eventually intramolecular SN2 reaction to the corresponding piperidine ring. Piperidinose 4 proved to be a poor glycosidase inhibitor.
European Journal of Organic Chemistry, 2003
Assuming the transition state of glycosyltransferase inhibitors to be similar to those encountere... more Assuming the transition state of glycosyltransferase inhibitors to be similar to those encountered with potent glycosidase inhibitors − i.e. a flattened conformation with a positively charged anomeric centre − we worked out a synthesis of the D‐arabino‐configured phosphonic acid target molecule 2 derived from an imidazolo‐sugar. The key synthetic intermediate is the linear imidazolo L‐xylo compound 10 which could be obtained, either from L‐threo precursor 6 by a coupling reaction with imidazole derivative 5, or from L‐sorbose. A multi‐step and site specific iodination of 10 gave the mono‐iodo‐L‐xylo derivative 14 which was cyclised to the D‐arabino‐configured bicyclic azasugar 15. Phosphorylation of the Grignard derivative of the latter, followed by mono‐esterification with citronellol along with some protection‐deprotection steps led to target molecule 2. The potential inhibitor 2 is supposed to be protonated at its most basic N atom by a carboxylic acid residue in the arabinosyl‐t...
European Journal of Organic Chemistry, 2002
ABSTRACT The syntheses of the imidazolo-pyrrolidino-pentoses ent-2 (L-arabino), 3 (D-xylo), 4 (D-... more ABSTRACT The syntheses of the imidazolo-pyrrolidino-pentoses ent-2 (L-arabino), 3 (D-xylo), 4 (D-lyxo), ent-4 (L-lyxo), and 5 (D-ribo) are reported, completing the series of all eight possible stereomers. The corresponding five linear imidazolo sugar precursors were prepared by nucleophilic addition of C(4)-metallated imidazole derivatives to the appropriately configured and protected aldotetroses. Cyclisation of the resulting linear imidazolo-carbohydrates was performed by means of intramolecular Walden inversion processes, followed by deprotection to afford the five target imidazolo-sugars. Three of the four D-configured stereomers proved to be good to moderate glycosidase inhibitors, as determined by Michaelis−Menten kinetics.
European Journal of Organic Chemistry, 2001
The syntheses of all four imidazolo-piperidino-pentoses in the L-series ent-2 to ent-5, and of th... more The syntheses of all four imidazolo-piperidino-pentoses in the L-series ent-2 to ent-5, and of three out of the four possible stereomers in the D-series 3, 4, and 5, are reported. The linear imidazolo sugar precursors were prepared, either by double condensation of formamidine with protected aldohexoses, or by nucleophilic addition of a lithiated imidazole derivative to protected aldotetroses. Cyclisation of these linear imidazolo-carbohydrates was performed by intramolecular SN2 reactions. These were followed by deprotection to the target molecules. The four pairs of opposite enantiomers showed pronounced mirror-image-type Cotton effects in their CD spectra. All stereomers of the D-series show a negative rotatory power ([α]D), while the stereomers of the L-series show a positive one. None of the eight imidazolo sugars inhibited the replication of HIV-1. Some of them proved to be rather selective but only moderately potent inhibitors of α-glycosidases, as determined by Michaelis-Menten kinetics.
European Journal of Organic Chemistry, 1999
ABSTRACT Some naturally occurring carbohydrates, of which several hydroxy groups had been selecti... more ABSTRACT Some naturally occurring carbohydrates, of which several hydroxy groups had been selectively protected, were condensed with formamidine to give the expected imidazole derivatives in the D-arabino (9), D-lyxo (12), L-xylo (17), D-threo (21), and in the L- and D-erythro (24) series. Introduction of a strong leaving group at the remaining free alcohol function of these products led at once to intramolecular SN2 cyclisation to the corresponding bicyclic aza sugar derivatives. This was followed by total deprotection to give the target aza sugars in the L-xylo (7), L-ribo (14), D-arabino (19), as well as in the D-threo (22) and the L- and D-erythro (26) series. Inhibitory assays with four glycosidases showed that the D-arabino aza sugar 19 is the only potent inhibitor (for an α-mannosidase of jack bean).
Carbohydrate Research, 1994
Chemistry - A European Journal, 2003
The key step in the trans-selective modification of the Wittig reaction is the alpha-lithiation o... more The key step in the trans-selective modification of the Wittig reaction is the alpha-lithiation of the lithium bromide coordinated ylide-aldehyde adduct (the so-called "P-betaine"). Only phenyllithium effects this deprotonation rapidly and cleanly. Alkyllithiums (in particular, butyl-, sec-butyl-, and tert-butyllithium) react only sluggishly and incompletely, being tied up in very stable mixed aggregates with the lithium alkoxide part of the betaines.
Chemical Communications
The manuscript describes studies on the radical tandem reaction involving Giese reaction followed... more The manuscript describes studies on the radical tandem reaction involving Giese reaction followed by HWE olefination.
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.
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.
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.
Pharmacological Reports, 2018
Background: The development of multidrug resistance to chemotherapy remains a challenge in the tr... more Background: The development of multidrug resistance to chemotherapy remains a challenge in the treatment of cancer and is a major factor causing failure of many forms of chemotherapy. The ATP binding cassette (ABC) family of proteins are efflux pumps that transport various potentially dangerous substances out of the cells. Several of the ABC transporters are related to chemoresistance, as the rapidly dividing malignant cells use them to protect themselves from medical interventions. Inhibitors of ABC transporters have the potential to enhance the efficacy of anticancer drugs. Two new synthetic compounds, AD-06 and AD-013, were tested as possible multidrug resistance inhibitors in MCF-7 cells. Methods: The cytotoxicity of new compounds was tested in MCF-7 and MCF-10A cell lines using the MTT method. Gene expression was measured by real-time PCR and changes in the protein levels were evaluated by flow cytometry and ELISA. A method based on the use of a fluorescent dye, being a marker of the ABC transporter activity, was used for screening the tested compounds as potential multidrug resistance inhibitors. Results: AD-06 and AD-013 down-regulated NF-κB mRNA levels and decreased the population of cells with activated NF-κB. Both compounds were found to be strong ABCB1 and ABCG2 transporter inhibitors. They showed synergistic effects when incubated with taxol or oxaliplatin. Conclusions: α-Methylene-γand-δ-lactones AD-06 and AD-013 are promising lead structures for further development as multidrug resistance inhibitors.
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.
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.
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.
Chemical Communications, 2008
Carbohydrate Research, 1994
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.
Tetrahedron, 2003
Carbohydrates Carbohydrates U 0500 Stereocontrolled Synthesis of Imidazolo[1,5]hexopiperidinoses ... more Carbohydrates Carbohydrates U 0500 Stereocontrolled Synthesis of Imidazolo[1,5]hexopiperidinoses and Imidazol-4(5)-yl-C-glycosides.-The synthesis of five imidazolohexopiperidinoses and three imidazolyl-C-glycosides is presented, involving an SN2-type cyclization of suitably substituted imidazolylpentitols. The reaction outcome is strongly influenced by steric requirements. Thus, imidazolohexopiperidinoses (VI), (X) and (XII) are readily formed in the L-galacto, D-ido, D-gulo and D-manno series, while their formation is suppressed in the L-talo and D-gluco series and imidazolyl-C-glycosides (VIII), (XV) and (XVI) are obtained instead.
Tetrahedron, 2007
ABSTRACT A new route for the synthesis of imidazolosugars—6-deoxyimidazolopiperidinoses 1 and 2 a... more ABSTRACT A new route for the synthesis of imidazolosugars—6-deoxyimidazolopiperidinoses 1 and 2 and 7-deoxyimidazoloazepanoses 3 and 4 in two enantiomerical forms—is reported. The new synthetic approach is based on two key reactions: (i) stereocontrolled Wittig Z-olefination of an imidazolecarbaldehyde with phosphoranes containing one chiral centre, obtained from (S)- and (R)-1,2,4-butantriol; (ii) diastereoselective cis-dihydroxylation of previously obtained olefins. All synthesised imidazolosugars were evaluated as potential inhibitors of glycosidases.
Tetrahedron, 1998
ABSTRACT Imidazolo-L-lyxo-piperidinose 4 was synthesised from the D-galactose derivative 8 by two... more ABSTRACT Imidazolo-L-lyxo-piperidinose 4 was synthesised from the D-galactose derivative 8 by two reaction sequences, via removal of a terminal carbon atom, stepwise incorporation of an imidazole moiety, and eventually intramolecular SN2 reaction to the corresponding piperidine ring. Piperidinose 4 proved to be a poor glycosidase inhibitor.
European Journal of Organic Chemistry, 2003
Assuming the transition state of glycosyltransferase inhibitors to be similar to those encountere... more Assuming the transition state of glycosyltransferase inhibitors to be similar to those encountered with potent glycosidase inhibitors − i.e. a flattened conformation with a positively charged anomeric centre − we worked out a synthesis of the D‐arabino‐configured phosphonic acid target molecule 2 derived from an imidazolo‐sugar. The key synthetic intermediate is the linear imidazolo L‐xylo compound 10 which could be obtained, either from L‐threo precursor 6 by a coupling reaction with imidazole derivative 5, or from L‐sorbose. A multi‐step and site specific iodination of 10 gave the mono‐iodo‐L‐xylo derivative 14 which was cyclised to the D‐arabino‐configured bicyclic azasugar 15. Phosphorylation of the Grignard derivative of the latter, followed by mono‐esterification with citronellol along with some protection‐deprotection steps led to target molecule 2. The potential inhibitor 2 is supposed to be protonated at its most basic N atom by a carboxylic acid residue in the arabinosyl‐t...
European Journal of Organic Chemistry, 2002
ABSTRACT The syntheses of the imidazolo-pyrrolidino-pentoses ent-2 (L-arabino), 3 (D-xylo), 4 (D-... more ABSTRACT The syntheses of the imidazolo-pyrrolidino-pentoses ent-2 (L-arabino), 3 (D-xylo), 4 (D-lyxo), ent-4 (L-lyxo), and 5 (D-ribo) are reported, completing the series of all eight possible stereomers. The corresponding five linear imidazolo sugar precursors were prepared by nucleophilic addition of C(4)-metallated imidazole derivatives to the appropriately configured and protected aldotetroses. Cyclisation of the resulting linear imidazolo-carbohydrates was performed by means of intramolecular Walden inversion processes, followed by deprotection to afford the five target imidazolo-sugars. Three of the four D-configured stereomers proved to be good to moderate glycosidase inhibitors, as determined by Michaelis−Menten kinetics.
European Journal of Organic Chemistry, 2001
The syntheses of all four imidazolo-piperidino-pentoses in the L-series ent-2 to ent-5, and of th... more The syntheses of all four imidazolo-piperidino-pentoses in the L-series ent-2 to ent-5, and of three out of the four possible stereomers in the D-series 3, 4, and 5, are reported. The linear imidazolo sugar precursors were prepared, either by double condensation of formamidine with protected aldohexoses, or by nucleophilic addition of a lithiated imidazole derivative to protected aldotetroses. Cyclisation of these linear imidazolo-carbohydrates was performed by intramolecular SN2 reactions. These were followed by deprotection to the target molecules. The four pairs of opposite enantiomers showed pronounced mirror-image-type Cotton effects in their CD spectra. All stereomers of the D-series show a negative rotatory power ([α]D), while the stereomers of the L-series show a positive one. None of the eight imidazolo sugars inhibited the replication of HIV-1. Some of them proved to be rather selective but only moderately potent inhibitors of α-glycosidases, as determined by Michaelis-Menten kinetics.
European Journal of Organic Chemistry, 1999
ABSTRACT Some naturally occurring carbohydrates, of which several hydroxy groups had been selecti... more ABSTRACT Some naturally occurring carbohydrates, of which several hydroxy groups had been selectively protected, were condensed with formamidine to give the expected imidazole derivatives in the D-arabino (9), D-lyxo (12), L-xylo (17), D-threo (21), and in the L- and D-erythro (24) series. Introduction of a strong leaving group at the remaining free alcohol function of these products led at once to intramolecular SN2 cyclisation to the corresponding bicyclic aza sugar derivatives. This was followed by total deprotection to give the target aza sugars in the L-xylo (7), L-ribo (14), D-arabino (19), as well as in the D-threo (22) and the L- and D-erythro (26) series. Inhibitory assays with four glycosidases showed that the D-arabino aza sugar 19 is the only potent inhibitor (for an α-mannosidase of jack bean).
Carbohydrate Research, 1994
Chemistry - A European Journal, 2003
The key step in the trans-selective modification of the Wittig reaction is the alpha-lithiation o... more The key step in the trans-selective modification of the Wittig reaction is the alpha-lithiation of the lithium bromide coordinated ylide-aldehyde adduct (the so-called "P-betaine"). Only phenyllithium effects this deprotonation rapidly and cleanly. Alkyllithiums (in particular, butyl-, sec-butyl-, and tert-butyllithium) react only sluggishly and incompletely, being tied up in very stable mixed aggregates with the lithium alkoxide part of the betaines.
Chemical Communications
The manuscript describes studies on the radical tandem reaction involving Giese reaction followed... more The manuscript describes studies on the radical tandem reaction involving Giese reaction followed by HWE olefination.
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.
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.
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.
Pharmacological Reports, 2018
Background: The development of multidrug resistance to chemotherapy remains a challenge in the tr... more Background: The development of multidrug resistance to chemotherapy remains a challenge in the treatment of cancer and is a major factor causing failure of many forms of chemotherapy. The ATP binding cassette (ABC) family of proteins are efflux pumps that transport various potentially dangerous substances out of the cells. Several of the ABC transporters are related to chemoresistance, as the rapidly dividing malignant cells use them to protect themselves from medical interventions. Inhibitors of ABC transporters have the potential to enhance the efficacy of anticancer drugs. Two new synthetic compounds, AD-06 and AD-013, were tested as possible multidrug resistance inhibitors in MCF-7 cells. Methods: The cytotoxicity of new compounds was tested in MCF-7 and MCF-10A cell lines using the MTT method. Gene expression was measured by real-time PCR and changes in the protein levels were evaluated by flow cytometry and ELISA. A method based on the use of a fluorescent dye, being a marker of the ABC transporter activity, was used for screening the tested compounds as potential multidrug resistance inhibitors. Results: AD-06 and AD-013 down-regulated NF-κB mRNA levels and decreased the population of cells with activated NF-κB. Both compounds were found to be strong ABCB1 and ABCG2 transporter inhibitors. They showed synergistic effects when incubated with taxol or oxaliplatin. Conclusions: α-Methylene-γand-δ-lactones AD-06 and AD-013 are promising lead structures for further development as multidrug resistance inhibitors.