TY  - DATA
AU  - Pitts, Amanda L.
AU  - Wriglesworth, Alisdair
AU  - Sun, Xue-Zhong
AU  - Calladine, James A.
AU  - Zarić, Snežana D.
AU  - George, Michael W.
AU  - Hall, Michael B.
PY  - 2014
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/3685
PB  - Amer Chemical Soc, Washington
T2  - Journal of the American Chemical Society
T1  - Supplementary data for the article: Pitts, A. L.; Wriglesworth, A.; Sun, X.-Z.; Calladine, J. A.; Zarić, S. D.; George, M. W.; Hall, M. B. Carbon-Hydrogen Activation of Cycloalkanes by Cyclopentadienylcarbonylrhodium-A Lifetime Enigma. Journal of the American Chemical Society 2014, 136 (24), 8614–8625. https://doi.org/10.1021/ja5014773
UR  - https://hdl.handle.net/21.15107/rcub_cherry_3685
ER  - 

@misc{
author = "Pitts, Amanda L. and Wriglesworth, Alisdair and Sun, Xue-Zhong and Calladine, James A. and Zarić, Snežana D. and George, Michael W. and Hall, Michael B.",
year = "2014",
publisher = "Amer Chemical Soc, Washington",
journal = "Journal of the American Chemical Society",
title = "Supplementary data for the article: Pitts, A. L.; Wriglesworth, A.; Sun, X.-Z.; Calladine, J. A.; Zarić, S. D.; George, M. W.; Hall, M. B. Carbon-Hydrogen Activation of Cycloalkanes by Cyclopentadienylcarbonylrhodium-A Lifetime Enigma. Journal of the American Chemical Society 2014, 136 (24), 8614–8625. https://doi.org/10.1021/ja5014773",
url = "https://hdl.handle.net/21.15107/rcub_cherry_3685"
}

Pitts, A. L., Wriglesworth, A., Sun, X., Calladine, J. A., Zarić, S. D., George, M. W.,& Hall, M. B.. (2014). Supplementary data for the article: Pitts, A. L.; Wriglesworth, A.; Sun, X.-Z.; Calladine, J. A.; Zarić, S. D.; George, M. W.; Hall, M. B. Carbon-Hydrogen Activation of Cycloalkanes by Cyclopentadienylcarbonylrhodium-A Lifetime Enigma. Journal of the American Chemical Society 2014, 136 (24), 8614–8625. https://doi.org/10.1021/ja5014773. in Journal of the American Chemical Society
Amer Chemical Soc, Washington..
https://hdl.handle.net/21.15107/rcub_cherry_3685

Pitts AL, Wriglesworth A, Sun X, Calladine JA, Zarić SD, George MW, Hall MB. Supplementary data for the article: Pitts, A. L.; Wriglesworth, A.; Sun, X.-Z.; Calladine, J. A.; Zarić, S. D.; George, M. W.; Hall, M. B. Carbon-Hydrogen Activation of Cycloalkanes by Cyclopentadienylcarbonylrhodium-A Lifetime Enigma. Journal of the American Chemical Society 2014, 136 (24), 8614–8625. https://doi.org/10.1021/ja5014773. in Journal of the American Chemical Society. 2014;.
https://hdl.handle.net/21.15107/rcub_cherry_3685 .

Pitts, Amanda L., Wriglesworth, Alisdair, Sun, Xue-Zhong, Calladine, James A., Zarić, Snežana D., George, Michael W., Hall, Michael B., "Supplementary data for the article: Pitts, A. L.; Wriglesworth, A.; Sun, X.-Z.; Calladine, J. A.; Zarić, S. D.; George, M. W.; Hall, M. B. Carbon-Hydrogen Activation of Cycloalkanes by Cyclopentadienylcarbonylrhodium-A Lifetime Enigma. Journal of the American Chemical Society 2014, 136 (24), 8614–8625. https://doi.org/10.1021/ja5014773" in Journal of the American Chemical Society (2014),
https://hdl.handle.net/21.15107/rcub_cherry_3685 .

TY  - JOUR
AU  - Pitts, Amanda L.
AU  - Wriglesworth, Alisdair
AU  - Sun, Xue-Zhong
AU  - Calladine, James A.
AU  - Zarić, Snežana D.
AU  - George, Michael W.
AU  - Hall, Michael B.
PY  - 2014
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/1792
AB  - Carbon-hydrogen bond activation reactions of four cycloalkanes (C5H10, C6H12, C7H14, and C8H16) by the Cp'Rh(CO) fragments (Cp' = eta(5)-C5H5 (Cp) or eta(5)-C5Me5 (Cp*)) were modeled theoretically by combining density functional and coupled cluster theories, and their reaction rates were measured by fast time-resolved infrared spectroscopy. The reaction has two steps, starting with the formation of a a-complex intermediate, followed by oxidative addition of the C-H bond by the rhodium. A range of a-complex stabilities among the electronically unique C-H bonds in a cycloalkane were calculated and are related to the individual strengths of the C-H bond's interactions with the Rh fragment and the steric repulsion that is incurred upon forming the specific a-complex. The unexpectedly large increase in the lifetimes of the a-complexes from cyclohexane to cycloheptane was predicted to be due to the large range of stabilities of the different sigma-complexes found for cycloheptane.. The reaction lifetimes were simulated with two mechanisms, with and without migrations among the different complexes, to determine if ring migrations prior to C-H activation were influencing the rate. Both mechanisms predicted similar lifetimes for cyclopentane, cyclohexane, and, to a lesser extent, cycloheptane, suggesting ring migrations do not have a large impact on the rate of C-H activation for these cycloalkanes. For cyclooctane, the inclusion of ring migrations in the reaction mechanism led to a more accurate prediction of the lifetime, indicating that ring migrations did have an effect on the rate of C-H activation for this alkane, and that migration among the a-complexes is faster than the C-H activation for this larger cycloalkane.
PB  - Amer Chemical Soc, Washington
T2  - Journal of the American Chemical Society
T1  - Carbon-Hydrogen Activation of Cycloalkanes by Cyclopentadienylcarbonylrhodium-A Lifetime Enigma
VL  - 136
IS  - 24
SP  - 8614
EP  - 8625
DO  - 10.1021/ja5014773
ER  - 

@article{
author = "Pitts, Amanda L. and Wriglesworth, Alisdair and Sun, Xue-Zhong and Calladine, James A. and Zarić, Snežana D. and George, Michael W. and Hall, Michael B.",
year = "2014",
abstract = "Carbon-hydrogen bond activation reactions of four cycloalkanes (C5H10, C6H12, C7H14, and C8H16) by the Cp'Rh(CO) fragments (Cp' = eta(5)-C5H5 (Cp) or eta(5)-C5Me5 (Cp*)) were modeled theoretically by combining density functional and coupled cluster theories, and their reaction rates were measured by fast time-resolved infrared spectroscopy. The reaction has two steps, starting with the formation of a a-complex intermediate, followed by oxidative addition of the C-H bond by the rhodium. A range of a-complex stabilities among the electronically unique C-H bonds in a cycloalkane were calculated and are related to the individual strengths of the C-H bond's interactions with the Rh fragment and the steric repulsion that is incurred upon forming the specific a-complex. The unexpectedly large increase in the lifetimes of the a-complexes from cyclohexane to cycloheptane was predicted to be due to the large range of stabilities of the different sigma-complexes found for cycloheptane.. The reaction lifetimes were simulated with two mechanisms, with and without migrations among the different complexes, to determine if ring migrations prior to C-H activation were influencing the rate. Both mechanisms predicted similar lifetimes for cyclopentane, cyclohexane, and, to a lesser extent, cycloheptane, suggesting ring migrations do not have a large impact on the rate of C-H activation for these cycloalkanes. For cyclooctane, the inclusion of ring migrations in the reaction mechanism led to a more accurate prediction of the lifetime, indicating that ring migrations did have an effect on the rate of C-H activation for this alkane, and that migration among the a-complexes is faster than the C-H activation for this larger cycloalkane.",
publisher = "Amer Chemical Soc, Washington",
journal = "Journal of the American Chemical Society",
title = "Carbon-Hydrogen Activation of Cycloalkanes by Cyclopentadienylcarbonylrhodium-A Lifetime Enigma",
volume = "136",
number = "24",
pages = "8614-8625",
doi = "10.1021/ja5014773"
}

Pitts, A. L., Wriglesworth, A., Sun, X., Calladine, J. A., Zarić, S. D., George, M. W.,& Hall, M. B.. (2014). Carbon-Hydrogen Activation of Cycloalkanes by Cyclopentadienylcarbonylrhodium-A Lifetime Enigma. in Journal of the American Chemical Society
Amer Chemical Soc, Washington., 136(24), 8614-8625.
https://doi.org/10.1021/ja5014773

Pitts AL, Wriglesworth A, Sun X, Calladine JA, Zarić SD, George MW, Hall MB. Carbon-Hydrogen Activation of Cycloalkanes by Cyclopentadienylcarbonylrhodium-A Lifetime Enigma. in Journal of the American Chemical Society. 2014;136(24):8614-8625.
doi:10.1021/ja5014773 .

Pitts, Amanda L., Wriglesworth, Alisdair, Sun, Xue-Zhong, Calladine, James A., Zarić, Snežana D., George, Michael W., Hall, Michael B., "Carbon-Hydrogen Activation of Cycloalkanes by Cyclopentadienylcarbonylrhodium-A Lifetime Enigma" in Journal of the American Chemical Society, 136, no. 24 (2014):8614-8625,
https://doi.org/10.1021/ja5014773 . .

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  - Chamberlain, Thomas W.
AU  - Pfeiffer, Rudolf
AU  - Howells, Jonathan
AU  - Peterlik, Herwig
AU  - Kuzmany, Hans
AU  - Kraeutler, Bernhard
AU  - Da Ros, Tatiana
AU  - Melle-Franco, Manuel
AU  - Zerbetto, Francesco
AU  - Milić, Dragana
AU  - Khlobystov, Andrei N.
PY  - 2012
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/1550
AB  - A range of mono- and bis-functionalised fullerenes have been synthesised and inserted into single-walled carbon nanotubes. The effect of the size and shape of the functional groups of the fullerenes on the resultant 1D arrays formed within the nanotubes was investigated by high resolution transmission electron microscopy and X-ray diffraction. The addition of non-planar, sterically bulky chains to the fullerene cage results in highly ordered 1D structures in which the fullerenes are evenly spaced along the internal nanotube cavity. Theoretical calculations reveal that the functional groups interact with neighbouring fullerene cages to space the fullerenes evenly within the confines of the nanotube. The addition of two functional groups to opposite sides of the fullerene cages results in a further increase in the separation of the fullerene cages within the nanotubes at the cost of lower nanotube filling rates.
PB  - Royal Soc Chemistry, Cambridge
T2  - Nanoscale
T1  - Engineering molecular chains in carbon nanotubes
VL  - 4
IS  - 23
SP  - 7540
EP  - 7548
DO  - 10.1039/c2nr32571c
ER  - 

@article{
author = "Chamberlain, Thomas W. and Pfeiffer, Rudolf and Howells, Jonathan and Peterlik, Herwig and Kuzmany, Hans and Kraeutler, Bernhard and Da Ros, Tatiana and Melle-Franco, Manuel and Zerbetto, Francesco and Milić, Dragana and Khlobystov, Andrei N.",
year = "2012",
abstract = "A range of mono- and bis-functionalised fullerenes have been synthesised and inserted into single-walled carbon nanotubes. The effect of the size and shape of the functional groups of the fullerenes on the resultant 1D arrays formed within the nanotubes was investigated by high resolution transmission electron microscopy and X-ray diffraction. The addition of non-planar, sterically bulky chains to the fullerene cage results in highly ordered 1D structures in which the fullerenes are evenly spaced along the internal nanotube cavity. Theoretical calculations reveal that the functional groups interact with neighbouring fullerene cages to space the fullerenes evenly within the confines of the nanotube. The addition of two functional groups to opposite sides of the fullerene cages results in a further increase in the separation of the fullerene cages within the nanotubes at the cost of lower nanotube filling rates.",
publisher = "Royal Soc Chemistry, Cambridge",
journal = "Nanoscale",
title = "Engineering molecular chains in carbon nanotubes",
volume = "4",
number = "23",
pages = "7540-7548",
doi = "10.1039/c2nr32571c"
}

Chamberlain, T. W., Pfeiffer, R., Howells, J., Peterlik, H., Kuzmany, H., Kraeutler, B., Da Ros, T., Melle-Franco, M., Zerbetto, F., Milić, D.,& Khlobystov, A. N.. (2012). Engineering molecular chains in carbon nanotubes. in Nanoscale
Royal Soc Chemistry, Cambridge., 4(23), 7540-7548.
https://doi.org/10.1039/c2nr32571c

Chamberlain TW, Pfeiffer R, Howells J, Peterlik H, Kuzmany H, Kraeutler B, Da Ros T, Melle-Franco M, Zerbetto F, Milić D, Khlobystov AN. Engineering molecular chains in carbon nanotubes. in Nanoscale. 2012;4(23):7540-7548.
doi:10.1039/c2nr32571c .

Chamberlain, Thomas W., Pfeiffer, Rudolf, Howells, Jonathan, Peterlik, Herwig, Kuzmany, Hans, Kraeutler, Bernhard, Da Ros, Tatiana, Melle-Franco, Manuel, Zerbetto, Francesco, Milić, Dragana, Khlobystov, Andrei N., "Engineering molecular chains in carbon nanotubes" in Nanoscale, 4, no. 23 (2012):7540-7548,
https://doi.org/10.1039/c2nr32571c . .

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 . .