TY  - JOUR
AU  - Trmčić, Milena
AU  - Chadbourne, Frances L.
AU  - Brear, Paul M.
AU  - Denny, Paul W.
AU  - Cobb, Steven L.
AU  - Hodgson, David R. W.
PY  - 2013
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/1620
AB  - We recently reported the use of PSCl3 for the thiophosphorylation of alkylamines where the resulting N-thiophosphoramidate ions could be readily S-alkylated (Chem. Commun., 2011, 47, 6156-6158.). Herein we report the development of this methodology using amino acid, amino sugar, aminonucleoside and aniline substrates. The hydrolysis properties of N-thiophosphoramidate ions and their reactivities towards alkylating agents are also explored. In addition, we demonstrate the application of our approach to the preparation of a small library of compounds, including quinoline-based N,S-dialkylthiophosphoramidates which were tested for antileishmanial activity.
PB  - Royal Soc Chemistry, Cambridge
T2  - Organic and Biomolecular Chemistry
T1  - Aqueous synthesis of N,S-dialkylthiophosphoramidates: design, optimisation and application to library construction and antileishmanial testing
VL  - 11
IS  - 16
SP  - 2660
EP  - 2675
DO  - 10.1039/c3ob27448a
ER  - 

@article{
author = "Trmčić, Milena and Chadbourne, Frances L. and Brear, Paul M. and Denny, Paul W. and Cobb, Steven L. and Hodgson, David R. W.",
year = "2013",
abstract = "We recently reported the use of PSCl3 for the thiophosphorylation of alkylamines where the resulting N-thiophosphoramidate ions could be readily S-alkylated (Chem. Commun., 2011, 47, 6156-6158.). Herein we report the development of this methodology using amino acid, amino sugar, aminonucleoside and aniline substrates. The hydrolysis properties of N-thiophosphoramidate ions and their reactivities towards alkylating agents are also explored. In addition, we demonstrate the application of our approach to the preparation of a small library of compounds, including quinoline-based N,S-dialkylthiophosphoramidates which were tested for antileishmanial activity.",
publisher = "Royal Soc Chemistry, Cambridge",
journal = "Organic and Biomolecular Chemistry",
title = "Aqueous synthesis of N,S-dialkylthiophosphoramidates: design, optimisation and application to library construction and antileishmanial testing",
volume = "11",
number = "16",
pages = "2660-2675",
doi = "10.1039/c3ob27448a"
}

Trmčić, M., Chadbourne, F. L., Brear, P. M., Denny, P. W., Cobb, S. L.,& Hodgson, D. R. W.. (2013). Aqueous synthesis of N,S-dialkylthiophosphoramidates: design, optimisation and application to library construction and antileishmanial testing. in Organic and Biomolecular Chemistry
Royal Soc Chemistry, Cambridge., 11(16), 2660-2675.
https://doi.org/10.1039/c3ob27448a

Trmčić M, Chadbourne FL, Brear PM, Denny PW, Cobb SL, Hodgson DRW. Aqueous synthesis of N,S-dialkylthiophosphoramidates: design, optimisation and application to library construction and antileishmanial testing. in Organic and Biomolecular Chemistry. 2013;11(16):2660-2675.
doi:10.1039/c3ob27448a .

Trmčić, Milena, Chadbourne, Frances L., Brear, Paul M., Denny, Paul W., Cobb, Steven L., Hodgson, David R. W., "Aqueous synthesis of N,S-dialkylthiophosphoramidates: design, optimisation and application to library construction and antileishmanial testing" in Organic and Biomolecular Chemistry, 11, no. 16 (2013):2660-2675,
https://doi.org/10.1039/c3ob27448a . .

TY  - JOUR
AU  - Trmčić, Milena
AU  - Chadbourne, Frances L.
AU  - Brear, Paul M.
AU  - Denny, Paul W.
AU  - Cobb, Steven L.
AU  - Hodgson, David R. W.
PY  - 2013
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/2821
AB  - We recently reported the use of PSCl3 for the thiophosphorylation of alkylamines where the resulting N-thiophosphoramidate ions could be readily S-alkylated (Chem. Commun., 2011, 47, 6156-6158.). Herein we report the development of this methodology using amino acid, amino sugar, aminonucleoside and aniline substrates. The hydrolysis properties of N-thiophosphoramidate ions and their reactivities towards alkylating agents are also explored. In addition, we demonstrate the application of our approach to the preparation of a small library of compounds, including quinoline-based N,S-dialkylthiophosphoramidates which were tested for antileishmanial activity.
PB  - Royal Soc Chemistry, Cambridge
T2  - Organic and Biomolecular Chemistry
T1  - Aqueous synthesis of N,S-dialkylthiophosphoramidates: design, optimisation and application to library construction and antileishmanial testing
VL  - 11
IS  - 16
SP  - 2660
EP  - 2675
DO  - 10.1039/c3ob27448a
ER  - 

@article{
author = "Trmčić, Milena and Chadbourne, Frances L. and Brear, Paul M. and Denny, Paul W. and Cobb, Steven L. and Hodgson, David R. W.",
year = "2013",
abstract = "We recently reported the use of PSCl3 for the thiophosphorylation of alkylamines where the resulting N-thiophosphoramidate ions could be readily S-alkylated (Chem. Commun., 2011, 47, 6156-6158.). Herein we report the development of this methodology using amino acid, amino sugar, aminonucleoside and aniline substrates. The hydrolysis properties of N-thiophosphoramidate ions and their reactivities towards alkylating agents are also explored. In addition, we demonstrate the application of our approach to the preparation of a small library of compounds, including quinoline-based N,S-dialkylthiophosphoramidates which were tested for antileishmanial activity.",
publisher = "Royal Soc Chemistry, Cambridge",
journal = "Organic and Biomolecular Chemistry",
title = "Aqueous synthesis of N,S-dialkylthiophosphoramidates: design, optimisation and application to library construction and antileishmanial testing",
volume = "11",
number = "16",
pages = "2660-2675",
doi = "10.1039/c3ob27448a"
}

Trmčić, M., Chadbourne, F. L., Brear, P. M., Denny, P. W., Cobb, S. L.,& Hodgson, D. R. W.. (2013). Aqueous synthesis of N,S-dialkylthiophosphoramidates: design, optimisation and application to library construction and antileishmanial testing. in Organic and Biomolecular Chemistry
Royal Soc Chemistry, Cambridge., 11(16), 2660-2675.
https://doi.org/10.1039/c3ob27448a

Trmčić M, Chadbourne FL, Brear PM, Denny PW, Cobb SL, Hodgson DRW. Aqueous synthesis of N,S-dialkylthiophosphoramidates: design, optimisation and application to library construction and antileishmanial testing. in Organic and Biomolecular Chemistry. 2013;11(16):2660-2675.
doi:10.1039/c3ob27448a .

Trmčić, Milena, Chadbourne, Frances L., Brear, Paul M., Denny, Paul W., Cobb, Steven L., Hodgson, David R. W., "Aqueous synthesis of N,S-dialkylthiophosphoramidates: design, optimisation and application to library construction and antileishmanial testing" in Organic and Biomolecular Chemistry, 11, no. 16 (2013):2660-2675,
https://doi.org/10.1039/c3ob27448a . .

TY  - DATA
AU  - Trmčić, Milena
AU  - Chadbourne, Frances L.
AU  - Brear, Paul M.
AU  - Denny, Paul W.
AU  - Cobb, Steven L.
AU  - Hodgson, David R. W.
PY  - 2013
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/3468
PB  - Royal Soc Chemistry, Cambridge
T2  - Organic and Biomolecular Chemistry
T1  - Supplementary data for article: Trmčić, M.; Chadbourne, F. L.; Brear, P. M.; Denny, P. W.; Cobb, S. L.; Hodgson, D. R. W. Aqueous Synthesis of N,S-Dialkylthiophosphoramidates: Design, Optimisation and Application to Library Construction and Antileishmanial Testing. Organic and Biomolecular Chemistry 2013, 11 (16), 2660–2675. https://doi.org/10.1039/c3ob27448a
UR  - https://hdl.handle.net/21.15107/rcub_cherry_3468
ER  - 

@misc{
author = "Trmčić, Milena and Chadbourne, Frances L. and Brear, Paul M. and Denny, Paul W. and Cobb, Steven L. and Hodgson, David R. W.",
year = "2013",
publisher = "Royal Soc Chemistry, Cambridge",
journal = "Organic and Biomolecular Chemistry",
title = "Supplementary data for article: Trmčić, M.; Chadbourne, F. L.; Brear, P. M.; Denny, P. W.; Cobb, S. L.; Hodgson, D. R. W. Aqueous Synthesis of N,S-Dialkylthiophosphoramidates: Design, Optimisation and Application to Library Construction and Antileishmanial Testing. Organic and Biomolecular Chemistry 2013, 11 (16), 2660–2675. https://doi.org/10.1039/c3ob27448a",
url = "https://hdl.handle.net/21.15107/rcub_cherry_3468"
}

Trmčić, M., Chadbourne, F. L., Brear, P. M., Denny, P. W., Cobb, S. L.,& Hodgson, D. R. W.. (2013). Supplementary data for article: Trmčić, M.; Chadbourne, F. L.; Brear, P. M.; Denny, P. W.; Cobb, S. L.; Hodgson, D. R. W. Aqueous Synthesis of N,S-Dialkylthiophosphoramidates: Design, Optimisation and Application to Library Construction and Antileishmanial Testing. Organic and Biomolecular Chemistry 2013, 11 (16), 2660–2675. https://doi.org/10.1039/c3ob27448a. in Organic and Biomolecular Chemistry
Royal Soc Chemistry, Cambridge..
https://hdl.handle.net/21.15107/rcub_cherry_3468

Trmčić M, Chadbourne FL, Brear PM, Denny PW, Cobb SL, Hodgson DRW. Supplementary data for article: Trmčić, M.; Chadbourne, F. L.; Brear, P. M.; Denny, P. W.; Cobb, S. L.; Hodgson, D. R. W. Aqueous Synthesis of N,S-Dialkylthiophosphoramidates: Design, Optimisation and Application to Library Construction and Antileishmanial Testing. Organic and Biomolecular Chemistry 2013, 11 (16), 2660–2675. https://doi.org/10.1039/c3ob27448a. in Organic and Biomolecular Chemistry. 2013;.
https://hdl.handle.net/21.15107/rcub_cherry_3468 .

Trmčić, Milena, Chadbourne, Frances L., Brear, Paul M., Denny, Paul W., Cobb, Steven L., Hodgson, David R. W., "Supplementary data for article: Trmčić, M.; Chadbourne, F. L.; Brear, P. M.; Denny, P. W.; Cobb, S. L.; Hodgson, D. R. W. Aqueous Synthesis of N,S-Dialkylthiophosphoramidates: Design, Optimisation and Application to Library Construction and Antileishmanial Testing. Organic and Biomolecular Chemistry 2013, 11 (16), 2660–2675. https://doi.org/10.1039/c3ob27448a" in Organic and Biomolecular Chemistry (2013),
https://hdl.handle.net/21.15107/rcub_cherry_3468 .

TY  - JOUR
AU  - Trmčić, Milena
AU  - Hodgson, David R. W.
PY  - 2011
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/1344
AB  - An aqueous method for the preparation of N,S-dialkyl thiophosphoramidates is reported. Thiophosphorylation of alkylamines was performed using SPCl3 in aqueous reaction media, and the resulting thiophosphoramidate-S-anions were S-alkylated with soft electrophiles. Ranges of amines and electrophiles were explored.
PB  - Royal Soc Chemistry, Cambridge
T2  - Chemical Communications
T1  - Synthesis of thiophosphoramidates in water: Click chemistry for phosphates
VL  - 47
IS  - 21
SP  - 6156
EP  - 6158
DO  - 10.1039/c1cc11586c
ER  - 

@article{
author = "Trmčić, Milena and Hodgson, David R. W.",
year = "2011",
abstract = "An aqueous method for the preparation of N,S-dialkyl thiophosphoramidates is reported. Thiophosphorylation of alkylamines was performed using SPCl3 in aqueous reaction media, and the resulting thiophosphoramidate-S-anions were S-alkylated with soft electrophiles. Ranges of amines and electrophiles were explored.",
publisher = "Royal Soc Chemistry, Cambridge",
journal = "Chemical Communications",
title = "Synthesis of thiophosphoramidates in water: Click chemistry for phosphates",
volume = "47",
number = "21",
pages = "6156-6158",
doi = "10.1039/c1cc11586c"
}

Trmčić, M.,& Hodgson, D. R. W.. (2011). Synthesis of thiophosphoramidates in water: Click chemistry for phosphates. in Chemical Communications
Royal Soc Chemistry, Cambridge., 47(21), 6156-6158.
https://doi.org/10.1039/c1cc11586c

Trmčić M, Hodgson DRW. Synthesis of thiophosphoramidates in water: Click chemistry for phosphates. in Chemical Communications. 2011;47(21):6156-6158.
doi:10.1039/c1cc11586c .

Trmčić, Milena, Hodgson, David R. W., "Synthesis of thiophosphoramidates in water: Click chemistry for phosphates" in Chemical Communications, 47, no. 21 (2011):6156-6158,
https://doi.org/10.1039/c1cc11586c . .

TY  - JOUR
AU  - Trmčić, Milena
AU  - Hodgson, David R. W.
PY  - 2011
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/2819
AB  - An aqueous method for the preparation of N,S-dialkyl thiophosphoramidates is reported. Thiophosphorylation of alkylamines was performed using SPCl3 in aqueous reaction media, and the resulting thiophosphoramidate-S-anions were S-alkylated with soft electrophiles. Ranges of amines and electrophiles were explored.
PB  - Royal Soc Chemistry, Cambridge
T2  - Chemical Communications
T1  - Synthesis of thiophosphoramidates in water: Click chemistry for phosphates
VL  - 47
IS  - 21
SP  - 6156
EP  - 6158
DO  - 10.1039/c1cc11586c
ER  - 

@article{
author = "Trmčić, Milena and Hodgson, David R. W.",
year = "2011",
abstract = "An aqueous method for the preparation of N,S-dialkyl thiophosphoramidates is reported. Thiophosphorylation of alkylamines was performed using SPCl3 in aqueous reaction media, and the resulting thiophosphoramidate-S-anions were S-alkylated with soft electrophiles. Ranges of amines and electrophiles were explored.",
publisher = "Royal Soc Chemistry, Cambridge",
journal = "Chemical Communications",
title = "Synthesis of thiophosphoramidates in water: Click chemistry for phosphates",
volume = "47",
number = "21",
pages = "6156-6158",
doi = "10.1039/c1cc11586c"
}

Trmčić, M.,& Hodgson, D. R. W.. (2011). Synthesis of thiophosphoramidates in water: Click chemistry for phosphates. in Chemical Communications
Royal Soc Chemistry, Cambridge., 47(21), 6156-6158.
https://doi.org/10.1039/c1cc11586c

Trmčić M, Hodgson DRW. Synthesis of thiophosphoramidates in water: Click chemistry for phosphates. in Chemical Communications. 2011;47(21):6156-6158.
doi:10.1039/c1cc11586c .

Trmčić, Milena, Hodgson, David R. W., "Synthesis of thiophosphoramidates in water: Click chemistry for phosphates" in Chemical Communications, 47, no. 21 (2011):6156-6158,
https://doi.org/10.1039/c1cc11586c . .

TY  - JOUR
AU  - Trmčić, Milena
AU  - Hodgson, David R. W.
PY  - 2010
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/1108
AB  - Background: Heterobifunctional cross-linking agents are useful in both protein science and organic synthesis. Aminolysis of reactive esters in aqueous systems is often used in bioconjugation chemistry, but it must compete against hydrolysis processes. Here we study the kinetics of aminolysis and hydrolysis of 2-S-phosphorylacetate ester intermediates that result from displacement of bromide by a thiophosphate nucleophile from commonly used bromoacetate ester cross-linking agents. Results: We found cross-linking between uridine-5'-monophosphorothioate and D-glucosamine using N-hydroxybenzotriazole and N-hydroxysuccinimde bromoacetates to be ineffective. In order to gain insight into these shortfalls, 2-S-(5'-thiophosphoryluridine)acetic acid esters were prepared using p-nitrophenyl bromoacetate or m-nitrophenyl bromoacetate in combination with uridine-5'-monophosphorothioate. Kinetics of hydrolysis and aminolysis of the resulting p- and m-nitrophenyl 2-S-(5'-thiophosphoryluridine)acetates were determined by monitoring the formation of phenolate ions spectrophotometrically as a function of pH. The p- and m-nitrophenyl 2-S-(5'-thiophosphoryluridine)acetates showed similar reactivity profiles despite the significant difference in the pK(aH) values of their nitrophenolate leaving groups. Both were more reactive with respect to hydrolysis and aminolysis in comparison to their simple acetate progenitors, but their calculated selectivity towards aminolysis vs hydrolysis, while reasonable, would not lead to clean reactions that do not require purification. Extrapolations of the kinetic data were used to predict leaving group pK(a) values that could lead to improved selectivity towards aminolysis while retaining reasonable reaction times. Conclusions: Both p- and m-nitrophenyl 2-S-(5'-thiophosphoryluridine)acetates show some selectivity towards aminolysis over hydrolysis, with the m-nitrophenolate system displaying slightly better selectivity. Extrapolation of the data for hydrolysis and aminolysis of these esters suggests that the use of readily accessible trifluoroethyl 2-S-(5'-thiophosphoryluridine)acetate with a leaving group pK(aH) of 12.4 should afford better selectivity while maintaining reasonable reaction times. Kinetically, p- and m-nitrophenyl 2-S-(5'-thiophosphoryluridine)acetates show similar properties to o-nitrophenyl 2-S-ethylacetate, and show no evidence for intramolecular catalysis of hydrolysis or aminolysis by the phosphoryl groups.
PB  - Beilstein-Institut, Frankfurt Am Main
T2  - Beilstein Journal of Organic Chemistry
T1  - Kinetic studies and predictions on the hydrolysis and aminolysis of esters of 2-S-phosphorylacetates
VL  - 6
SP  - 732
EP  - 741
DO  - 10.3762/bjoc.6.87
ER  - 

@article{
author = "Trmčić, Milena and Hodgson, David R. W.",
year = "2010",
abstract = "Background: Heterobifunctional cross-linking agents are useful in both protein science and organic synthesis. Aminolysis of reactive esters in aqueous systems is often used in bioconjugation chemistry, but it must compete against hydrolysis processes. Here we study the kinetics of aminolysis and hydrolysis of 2-S-phosphorylacetate ester intermediates that result from displacement of bromide by a thiophosphate nucleophile from commonly used bromoacetate ester cross-linking agents. Results: We found cross-linking between uridine-5'-monophosphorothioate and D-glucosamine using N-hydroxybenzotriazole and N-hydroxysuccinimde bromoacetates to be ineffective. In order to gain insight into these shortfalls, 2-S-(5'-thiophosphoryluridine)acetic acid esters were prepared using p-nitrophenyl bromoacetate or m-nitrophenyl bromoacetate in combination with uridine-5'-monophosphorothioate. Kinetics of hydrolysis and aminolysis of the resulting p- and m-nitrophenyl 2-S-(5'-thiophosphoryluridine)acetates were determined by monitoring the formation of phenolate ions spectrophotometrically as a function of pH. The p- and m-nitrophenyl 2-S-(5'-thiophosphoryluridine)acetates showed similar reactivity profiles despite the significant difference in the pK(aH) values of their nitrophenolate leaving groups. Both were more reactive with respect to hydrolysis and aminolysis in comparison to their simple acetate progenitors, but their calculated selectivity towards aminolysis vs hydrolysis, while reasonable, would not lead to clean reactions that do not require purification. Extrapolations of the kinetic data were used to predict leaving group pK(a) values that could lead to improved selectivity towards aminolysis while retaining reasonable reaction times. Conclusions: Both p- and m-nitrophenyl 2-S-(5'-thiophosphoryluridine)acetates show some selectivity towards aminolysis over hydrolysis, with the m-nitrophenolate system displaying slightly better selectivity. Extrapolation of the data for hydrolysis and aminolysis of these esters suggests that the use of readily accessible trifluoroethyl 2-S-(5'-thiophosphoryluridine)acetate with a leaving group pK(aH) of 12.4 should afford better selectivity while maintaining reasonable reaction times. Kinetically, p- and m-nitrophenyl 2-S-(5'-thiophosphoryluridine)acetates show similar properties to o-nitrophenyl 2-S-ethylacetate, and show no evidence for intramolecular catalysis of hydrolysis or aminolysis by the phosphoryl groups.",
publisher = "Beilstein-Institut, Frankfurt Am Main",
journal = "Beilstein Journal of Organic Chemistry",
title = "Kinetic studies and predictions on the hydrolysis and aminolysis of esters of 2-S-phosphorylacetates",
volume = "6",
pages = "732-741",
doi = "10.3762/bjoc.6.87"
}

Trmčić, M.,& Hodgson, D. R. W.. (2010). Kinetic studies and predictions on the hydrolysis and aminolysis of esters of 2-S-phosphorylacetates. in Beilstein Journal of Organic Chemistry
Beilstein-Institut, Frankfurt Am Main., 6, 732-741.
https://doi.org/10.3762/bjoc.6.87

Trmčić M, Hodgson DRW. Kinetic studies and predictions on the hydrolysis and aminolysis of esters of 2-S-phosphorylacetates. in Beilstein Journal of Organic Chemistry. 2010;6:732-741.
doi:10.3762/bjoc.6.87 .

Trmčić, Milena, Hodgson, David R. W., "Kinetic studies and predictions on the hydrolysis and aminolysis of esters of 2-S-phosphorylacetates" in Beilstein Journal of Organic Chemistry, 6 (2010):732-741,
https://doi.org/10.3762/bjoc.6.87 . .

TY  - JOUR
AU  - Brear, Paul
AU  - Freeman, Gemma R.
AU  - Shankey, Mark C.
AU  - Trmčić, Milena
AU  - Hodgson, David R. W.
PY  - 2009
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/1006
AB  - We have developed simple, aqueous strategies, that avoid the use of protecting groups and chromatography, for the preparation of a series of 5'-substituted guanosine derivatives.
PB  - Royal Soc Chemistry, Cambridge
T2  - Chemical Communications
T1  - Aqueous methods for the preparation of 5 '-substituted guanosine derivatives
IS  - 33
SP  - 4980
EP  - 4981
DO  - 10.1039/b908727c
ER  - 

@article{
author = "Brear, Paul and Freeman, Gemma R. and Shankey, Mark C. and Trmčić, Milena and Hodgson, David R. W.",
year = "2009",
abstract = "We have developed simple, aqueous strategies, that avoid the use of protecting groups and chromatography, for the preparation of a series of 5'-substituted guanosine derivatives.",
publisher = "Royal Soc Chemistry, Cambridge",
journal = "Chemical Communications",
title = "Aqueous methods for the preparation of 5 '-substituted guanosine derivatives",
number = "33",
pages = "4980-4981",
doi = "10.1039/b908727c"
}

Brear, P., Freeman, G. R., Shankey, M. C., Trmčić, M.,& Hodgson, D. R. W.. (2009). Aqueous methods for the preparation of 5 '-substituted guanosine derivatives. in Chemical Communications
Royal Soc Chemistry, Cambridge.(33), 4980-4981.
https://doi.org/10.1039/b908727c

Brear P, Freeman GR, Shankey MC, Trmčić M, Hodgson DRW. Aqueous methods for the preparation of 5 '-substituted guanosine derivatives. in Chemical Communications. 2009;(33):4980-4981.
doi:10.1039/b908727c .

Brear, Paul, Freeman, Gemma R., Shankey, Mark C., Trmčić, Milena, Hodgson, David R. W., "Aqueous methods for the preparation of 5 '-substituted guanosine derivatives" in Chemical Communications, no. 33 (2009):4980-4981,
https://doi.org/10.1039/b908727c . .