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Effect of sulfonamidoethylenediamine substituents in RuII arene anticancer catalysts on transfer hydrogenation of coenzyme NAD+ by formate
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Chen, Feng, Soldevila-Barreda, Joan J., Romero-Canelón, Isolda, Coverdale, James P. C., Song, Ji-Inn, Clarkson, Guy J., Kasparkova, Jana, Habtemariam, Abraha, Brabec, Viktor, Wolny, Juliusz A., Schünemann, Volker and Sadler, P. J. (2018) Effect of sulfonamidoethylenediamine substituents in RuII arene anticancer catalysts on transfer hydrogenation of coenzyme NAD+ by formate. Dalton Transactions, 47 (21). 7178-7189 . doi:10.1039/C8DT00438B ISSN 1477-9234.
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Official URL: https://doi.org/10.1039/C8DT00438B
Abstract
A series of neutral pseudo-octahedral RuII sulfonamidoethylenediamine complexes [(η6-p-cym)Ru(N, N’)Cl] where N, N’ is N-(2-(R1,R2-amino)ethyl)-4-toluenesulfonamide (TsEn(R1,R2)) R1,R2 = Me,H (1); Me,Me (2); Et,H (3); benzyl,H (Bz, 4); 4-fluorobenzyl,H (4-F-Bz, 5) or naphthalen-2-ylmethyl,H (Naph, 6), were synthesised and characterised including the X-ray crystal structure of 3. These complexes catalyse the reduction of NAD+ regioselectively to 1, 4-NADH by using formate as hydride source. The catalytic efficiency depends markedly on the steric and electronic effects of the N-substitutent, with turnover frequencies (TOFs) increasing in the order: 1 < 2 < 3, 6 < 4, 5, achieving a TOF of 7.7 h-1 for 4 with a 95% yield of 1, 4-NADH. The reduction rate was highest between pH* (deuterated solvent) 6 and 7.5 and improved with an increase in formate concentration (TOF of 18.8 h-1, 140 mM formate). The calculations suggested initial substitution of an aqua ligand by formate, followed by hydride transfer to RuII and then to NAD+, and indicated specific interactions between the aqua complex and both NAD+ and NADH, the former allowing a preorganisation involving interaction between the aqua ligand, formate anion and the pyridine ring of NAD+. The complexes exhibited antiproliferative activity towards A2780 human ovarian cancer cells with IC50 values ranging from 1 to 31 μM, the most potent complex, [(η6-p-cym)Ru(TsEn(Bz,H))Cl] (4, IC50 = 1.0 ± 0.1 μM), having a potency similar to the anticancer drug cisplatin. Co-administration with sodium formate (2 mM), increased the potency of all complexes towards A2780 cells by 20-36%, with the greatest effect seen for complex 6.
Item Type: | Journal Article | ||||||||||||||||||||||||||||||
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Subjects: | Q Science > QD Chemistry R Medicine > RC Internal medicine > RC0254 Neoplasms. Tumors. Oncology (including Cancer) R Medicine > RS Pharmacy and materia medica |
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||||||||||||||||||||||||
Library of Congress Subject Headings (LCSH): | Antineoplastic agents, Nicotinamide, Coenzymes, Hydrogenation, Ovaries -- Cancer -- Treatment | ||||||||||||||||||||||||||||||
Journal or Publication Title: | Dalton Transactions | ||||||||||||||||||||||||||||||
Publisher: | Royal Society of Chemistry | ||||||||||||||||||||||||||||||
ISSN: | 1477-9234 | ||||||||||||||||||||||||||||||
Official Date: | 13 April 2018 | ||||||||||||||||||||||||||||||
Dates: |
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Volume: | 47 | ||||||||||||||||||||||||||||||
Number: | 21 | ||||||||||||||||||||||||||||||
Page Range: | 7178-7189 | ||||||||||||||||||||||||||||||
DOI: | 10.1039/C8DT00438B | ||||||||||||||||||||||||||||||
Status: | Peer Reviewed | ||||||||||||||||||||||||||||||
Publication Status: | Published | ||||||||||||||||||||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | ||||||||||||||||||||||||||||||
Date of first compliant deposit: | 30 May 2018 | ||||||||||||||||||||||||||||||
Date of first compliant Open Access: | 30 May 2018 | ||||||||||||||||||||||||||||||
RIOXX Funder/Project Grant: |
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