Synergistic Activation of Nitrite and Thiocarbonyl Compounds Affords NO and Sulfane Sulfur via (Per)thionitrite (SNO - /SSNO - ).

Autor: Kolliyedath G; School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram (IISER-Tvm) Thiruvananthapuram, 695551, Kerala, India., Sahana T; School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram (IISER-Tvm) Thiruvananthapuram, 695551, Kerala, India., Johnson SM; School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram (IISER-Tvm) Thiruvananthapuram, 695551, Kerala, India., Kundu S; School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram (IISER-Tvm) Thiruvananthapuram, 695551, Kerala, India.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2023 Dec 11; Vol. 62 (50), pp. e202313187. Date of Electronic Publication: 2023 Nov 09.
DOI: 10.1002/anie.202313187
Abstrakt: (Per)thionitrite (SNO - /SSNO - ) intermediates play vital roles in modulating nitric oxide (NO) and hydrogen sulfide (H 2 S) dependent bio-signalling processes. Whilst the previous preparations of such intermediates involved reactive H 2 S/HS - or sulfane sulfur (S 0 ) species, the present report reveals that relatively stable thiocarbonyl compounds (such as carbon disulfide (CS 2 ), thiocarbamate, thioacetic acid, and thioacetate) react with nitrite anion to yield SNO - /SSNO - . For instance, the reaction of CS 2 and nitrite anion (NO 2 - ) under ambient condition affords CO 2 and SNO - /SSNO - . A detailed investigation involving UV/Vis, FTIR, HRMS, and multinuclear NMR studies confirm the formation of SNO - /SSNO - , which are proposed to form through an initial nucleophilic attack by nitrite anion followed by a transnitrosation step. Notably, reactions of CS 2 and nitrite in the presence of thiol RSH show the formation of organic polysulfides R-S n -R, thereby illustrating that the thiocarbonyls are capable of influencing the pool of bioavailable sulfane sulfurs. Furthermore, the availability of both NO 2 - and thiocarbonyl motifs in the biological context hints at their synergistic metal-free activations leading to the generation of NO gas and various reactive sulfur species via SNO - /SSNO - .
(© 2023 Wiley-VCH GmbH.)
Databáze: MEDLINE
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