Dialkylaminodifluorosulfinium salts: XtalFluor-E and XtalFluor-M

(A) Failure of Hydrocinnamyl Alcohol with XtalFluor-M: The reaction of hydrocinnamyl alcohol with 2 or 1 in acetonitrile provided an intractable mixture. For this reaction to proceed, the addition of exogenous sources of fluoride, such as Et3N·3HF or Et3N·2HF, was necessary (B) Halogenation of Alcoh...

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Autor: Franconetti García, Antonio
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2013
País:España
Institución:Universidad de Sevilla (US)
Repositorio:idUS. Depósito de Investigación de la Universidad de Sevilla
OAI Identifier:oai:idus.us.es:11441/62903
Acceso en línea:http://hdl.handle.net/11441/62903
https://doi.org/10.1055/s-0032-1318499
Access Level:acceso abierto
Palabra clave:XtalFluor E
XtalFluor M
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spelling Dialkylaminodifluorosulfinium salts: XtalFluor-E and XtalFluor-MFranconetti García, AntonioXtalFluor EXtalFluor M(A) Failure of Hydrocinnamyl Alcohol with XtalFluor-M: The reaction of hydrocinnamyl alcohol with 2 or 1 in acetonitrile provided an intractable mixture. For this reaction to proceed, the addition of exogenous sources of fluoride, such as Et3N·3HF or Et3N·2HF, was necessary (B) Halogenation of Alcohols with XtalFluor Reagents: Reaction of primary, secondary and tertiary alcohols with 1 using Et3N·3HF as a promoter gave the fluorinated nucleophilic substitution products. The addition order was a key parameter in this reaction. To obtain good selectivity and stereochemical integrity, 1,8-diazabicycloundec-7-ene (DBU) had to be used together with the fluorination agents. 5 A mixture of fluorinated bridged biphenyl systems has been obtained from 3-hydroxyspirodienones by means of a XtalFluor-E-promoted rearrangement. When compound 2 was used instead of compound 1, substrate decomposition was observed. 6 Chlorination, bromination and iodination reaction of primary alcohols in good yield has been described using a combination of tetraethylammonium halide and XtalFluor- E. (C) Geminal Difluorination of Carbonyl Groups: L'Heureux et al. have reported the geminal difluorination of carbonyl groups of aldehydes and ketones. They demonstrated that compound 1 alone was incapable of performing such transformations.5,8 To obtain geminal difluorinated products, it was necessary to use a promoter and increase the temperature (e.g., CH 2Cl2 or 1,2-dichloroethane at reflux). (D) Fluorination Processes on Carbohydrate Derivatives: Fuchs and co-workers have recently reported the preparation of a fluorodisaccharide in excellent yield without side products using XtalFluor-E, thus eliminating the need for purification. 9 The effective preparation of glycosyl fluorides from thio-, seleno-, telluro- and glycosyl sulfoxides has been performed in 30 minutes by Williams and co-workers with evidence that fluoride is delivered by the tetrafluoroborate counterion (E) Enantioselective Ring Expansion of Prolinols: Direct ring expansion of N-alkyl prolinols to produce the corresponding 3-azidopiperidines in good and excellent regio-, diastereo- and enantioselectivity was achieved by using XtalFluor-E. Formation of an aziridinium intermediate which reacts with a nucleophile such as tetrabutylammonium azide (Bu4NN3) is proposed (F) Cyclodehydration Agents: Paquin and co-workers have recently reported 12 the use of 1 as a practical cyclodehydration agent to obtain 1,3,4-oxadiazoles among other nitrogen-containing heterocycles.13 The addition of acetic acid improved the yield and selectivity of the oxadiazole formation. (G) Activating Agents for Carboxylic Acids: Compound 1 has proved to be an efficient coupling agent for the synthesis of amides by activation of the carboxylic acid. 14 Moreover, this reaction is carried out with primary and secondary amines in good yield without epimerization or racemizationGeorg Thieme VerlagQuímica Orgánica2013info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfapplication/pdfhttp://hdl.handle.net/11441/62903https://doi.org/10.1055/s-0032-1318499reponame:idUS. Depósito de Investigación de la Universidad de Sevillainstname:Universidad de Sevilla (US)InglésSynlett, 24 (7), 891-892.http://dx.doi.org/10.1055/s-0032-1318499info:eu-repo/semantics/openAccessoai:idus.us.es:11441/629032026-06-17T12:51:07Z
dc.title.none.fl_str_mv Dialkylaminodifluorosulfinium salts: XtalFluor-E and XtalFluor-M
title Dialkylaminodifluorosulfinium salts: XtalFluor-E and XtalFluor-M
spellingShingle Dialkylaminodifluorosulfinium salts: XtalFluor-E and XtalFluor-M
Franconetti García, Antonio
XtalFluor E
XtalFluor M
title_short Dialkylaminodifluorosulfinium salts: XtalFluor-E and XtalFluor-M
title_full Dialkylaminodifluorosulfinium salts: XtalFluor-E and XtalFluor-M
title_fullStr Dialkylaminodifluorosulfinium salts: XtalFluor-E and XtalFluor-M
title_full_unstemmed Dialkylaminodifluorosulfinium salts: XtalFluor-E and XtalFluor-M
title_sort Dialkylaminodifluorosulfinium salts: XtalFluor-E and XtalFluor-M
dc.creator.none.fl_str_mv Franconetti García, Antonio
author Franconetti García, Antonio
author_facet Franconetti García, Antonio
author_role author
dc.contributor.none.fl_str_mv Química Orgánica
dc.subject.none.fl_str_mv XtalFluor E
XtalFluor M
topic XtalFluor E
XtalFluor M
description (A) Failure of Hydrocinnamyl Alcohol with XtalFluor-M: The reaction of hydrocinnamyl alcohol with 2 or 1 in acetonitrile provided an intractable mixture. For this reaction to proceed, the addition of exogenous sources of fluoride, such as Et3N·3HF or Et3N·2HF, was necessary (B) Halogenation of Alcohols with XtalFluor Reagents: Reaction of primary, secondary and tertiary alcohols with 1 using Et3N·3HF as a promoter gave the fluorinated nucleophilic substitution products. The addition order was a key parameter in this reaction. To obtain good selectivity and stereochemical integrity, 1,8-diazabicycloundec-7-ene (DBU) had to be used together with the fluorination agents. 5 A mixture of fluorinated bridged biphenyl systems has been obtained from 3-hydroxyspirodienones by means of a XtalFluor-E-promoted rearrangement. When compound 2 was used instead of compound 1, substrate decomposition was observed. 6 Chlorination, bromination and iodination reaction of primary alcohols in good yield has been described using a combination of tetraethylammonium halide and XtalFluor- E. (C) Geminal Difluorination of Carbonyl Groups: L'Heureux et al. have reported the geminal difluorination of carbonyl groups of aldehydes and ketones. They demonstrated that compound 1 alone was incapable of performing such transformations.5,8 To obtain geminal difluorinated products, it was necessary to use a promoter and increase the temperature (e.g., CH 2Cl2 or 1,2-dichloroethane at reflux). (D) Fluorination Processes on Carbohydrate Derivatives: Fuchs and co-workers have recently reported the preparation of a fluorodisaccharide in excellent yield without side products using XtalFluor-E, thus eliminating the need for purification. 9 The effective preparation of glycosyl fluorides from thio-, seleno-, telluro- and glycosyl sulfoxides has been performed in 30 minutes by Williams and co-workers with evidence that fluoride is delivered by the tetrafluoroborate counterion (E) Enantioselective Ring Expansion of Prolinols: Direct ring expansion of N-alkyl prolinols to produce the corresponding 3-azidopiperidines in good and excellent regio-, diastereo- and enantioselectivity was achieved by using XtalFluor-E. Formation of an aziridinium intermediate which reacts with a nucleophile such as tetrabutylammonium azide (Bu4NN3) is proposed (F) Cyclodehydration Agents: Paquin and co-workers have recently reported 12 the use of 1 as a practical cyclodehydration agent to obtain 1,3,4-oxadiazoles among other nitrogen-containing heterocycles.13 The addition of acetic acid improved the yield and selectivity of the oxadiazole formation. (G) Activating Agents for Carboxylic Acids: Compound 1 has proved to be an efficient coupling agent for the synthesis of amides by activation of the carboxylic acid. 14 Moreover, this reaction is carried out with primary and secondary amines in good yield without epimerization or racemization
publishDate 2013
dc.date.none.fl_str_mv 2013
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11441/62903
https://doi.org/10.1055/s-0032-1318499
url http://hdl.handle.net/11441/62903
https://doi.org/10.1055/s-0032-1318499
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Synlett, 24 (7), 891-892.
http://dx.doi.org/10.1055/s-0032-1318499
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Georg Thieme Verlag
publisher.none.fl_str_mv Georg Thieme Verlag
dc.source.none.fl_str_mv reponame:idUS. Depósito de Investigación de la Universidad de Sevilla
instname:Universidad de Sevilla (US)
instname_str Universidad de Sevilla (US)
reponame_str idUS. Depósito de Investigación de la Universidad de Sevilla
collection idUS. Depósito de Investigación de la Universidad de Sevilla
repository.name.fl_str_mv
repository.mail.fl_str_mv
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