Electrochemical bromination of peracetylated D-glucal: Effect of DMSO on chemoselectivity
Samo za registrovane korisnike
2010
Autori
Damljanovic, IvanVukicevic, Mirjana
Manojlović, Dragan D.
Šojić, Nešo
Buriez, Olivier
Vukicevic, Rastko D.
Članak u časopisu (Objavljena verzija)
Metapodaci
Prikaz svih podataka o dokumentuApstrakt
The electrochemical bromination of 3,4.6-tri-O-acetyl-D-glucal (1) has been investigated in dimethyl sulfoxide (DMSO) by cyclic voltammetry and preparative-scale electrolyses. In this solvent, the bromination involves a bromine-DMSO complex of the type [DMSO-Br](+) Br(-) whose reactivity towards 1 was clearly evidenced by cyclic voltammetry. Importantly, only the monobrominated glucose and mannose derivatives were obtained from electrolyses. This specific behavior was attributed to the nucleophilicity of DMSO that may react with the oxocarbenium intermediate preventing thus a possible second bromination of the transient species. The gluco/manno ratio, roughly equal to 30/70, indicated an electrophilic attack by [DMSO-Br](+) Br(-) preferentially from the beta side of the starting glycal for steric reasons. The treatment of the crude product obtained after the end of the electrolyses with acetic anhydride allowed the preparation of derivatives in which the anomeric carbon bears an acetox...y group. Based on both the cyclic voltammetry experiments and preparative-scale electrolyses, a mechanism is proposed for the bromination of peracetylated D-glucal in DMSO. These new and original results are of high interest in carbohydrate chemistry and especially for the preparation of new valuable oligosaccharides. (C) 2009 Elsevier Ltd. All rights reserved.
Ključne reči:
Bromination / Cyclic voltammetry / Electrosynthesis / Glucal / Sugar derivativesIzvor:
Electrochimica Acta, 2010, 55, 3, 965-969Izdavač:
- Pergamon-Elsevier Science Ltd, Oxford
Finansiranje / projekti:
- Ministry of Science and Environmental Protection of the Republic of Serbia [2042]
DOI: 10.1016/j.electacta.2009.09.057
ISSN: 0013-4686
WoS: 000274020200051
Scopus: 2-s2.0-70849109027
Kolekcije
Institucija/grupa
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Damljanovic, Ivan AU - Vukicevic, Mirjana AU - Manojlović, Dragan D. AU - Šojić, Nešo AU - Buriez, Olivier AU - Vukicevic, Rastko D. PY - 2010 UR - https://cherry.chem.bg.ac.rs/handle/123456789/1042 AB - The electrochemical bromination of 3,4.6-tri-O-acetyl-D-glucal (1) has been investigated in dimethyl sulfoxide (DMSO) by cyclic voltammetry and preparative-scale electrolyses. In this solvent, the bromination involves a bromine-DMSO complex of the type [DMSO-Br](+) Br(-) whose reactivity towards 1 was clearly evidenced by cyclic voltammetry. Importantly, only the monobrominated glucose and mannose derivatives were obtained from electrolyses. This specific behavior was attributed to the nucleophilicity of DMSO that may react with the oxocarbenium intermediate preventing thus a possible second bromination of the transient species. The gluco/manno ratio, roughly equal to 30/70, indicated an electrophilic attack by [DMSO-Br](+) Br(-) preferentially from the beta side of the starting glycal for steric reasons. The treatment of the crude product obtained after the end of the electrolyses with acetic anhydride allowed the preparation of derivatives in which the anomeric carbon bears an acetoxy group. Based on both the cyclic voltammetry experiments and preparative-scale electrolyses, a mechanism is proposed for the bromination of peracetylated D-glucal in DMSO. These new and original results are of high interest in carbohydrate chemistry and especially for the preparation of new valuable oligosaccharides. (C) 2009 Elsevier Ltd. All rights reserved. PB - Pergamon-Elsevier Science Ltd, Oxford T2 - Electrochimica Acta T1 - Electrochemical bromination of peracetylated D-glucal: Effect of DMSO on chemoselectivity VL - 55 IS - 3 SP - 965 EP - 969 DO - 10.1016/j.electacta.2009.09.057 ER -
@article{ author = "Damljanovic, Ivan and Vukicevic, Mirjana and Manojlović, Dragan D. and Šojić, Nešo and Buriez, Olivier and Vukicevic, Rastko D.", year = "2010", abstract = "The electrochemical bromination of 3,4.6-tri-O-acetyl-D-glucal (1) has been investigated in dimethyl sulfoxide (DMSO) by cyclic voltammetry and preparative-scale electrolyses. In this solvent, the bromination involves a bromine-DMSO complex of the type [DMSO-Br](+) Br(-) whose reactivity towards 1 was clearly evidenced by cyclic voltammetry. Importantly, only the monobrominated glucose and mannose derivatives were obtained from electrolyses. This specific behavior was attributed to the nucleophilicity of DMSO that may react with the oxocarbenium intermediate preventing thus a possible second bromination of the transient species. The gluco/manno ratio, roughly equal to 30/70, indicated an electrophilic attack by [DMSO-Br](+) Br(-) preferentially from the beta side of the starting glycal for steric reasons. The treatment of the crude product obtained after the end of the electrolyses with acetic anhydride allowed the preparation of derivatives in which the anomeric carbon bears an acetoxy group. Based on both the cyclic voltammetry experiments and preparative-scale electrolyses, a mechanism is proposed for the bromination of peracetylated D-glucal in DMSO. These new and original results are of high interest in carbohydrate chemistry and especially for the preparation of new valuable oligosaccharides. (C) 2009 Elsevier Ltd. All rights reserved.", publisher = "Pergamon-Elsevier Science Ltd, Oxford", journal = "Electrochimica Acta", title = "Electrochemical bromination of peracetylated D-glucal: Effect of DMSO on chemoselectivity", volume = "55", number = "3", pages = "965-969", doi = "10.1016/j.electacta.2009.09.057" }
Damljanovic, I., Vukicevic, M., Manojlović, D. D., Šojić, N., Buriez, O.,& Vukicevic, R. D.. (2010). Electrochemical bromination of peracetylated D-glucal: Effect of DMSO on chemoselectivity. in Electrochimica Acta Pergamon-Elsevier Science Ltd, Oxford., 55(3), 965-969. https://doi.org/10.1016/j.electacta.2009.09.057
Damljanovic I, Vukicevic M, Manojlović DD, Šojić N, Buriez O, Vukicevic RD. Electrochemical bromination of peracetylated D-glucal: Effect of DMSO on chemoselectivity. in Electrochimica Acta. 2010;55(3):965-969. doi:10.1016/j.electacta.2009.09.057 .
Damljanovic, Ivan, Vukicevic, Mirjana, Manojlović, Dragan D., Šojić, Nešo, Buriez, Olivier, Vukicevic, Rastko D., "Electrochemical bromination of peracetylated D-glucal: Effect of DMSO on chemoselectivity" in Electrochimica Acta, 55, no. 3 (2010):965-969, https://doi.org/10.1016/j.electacta.2009.09.057 . .