Trithioorthoester Exchange and Metathesis: New Tools for Dynamic Covalent Chemistry

Autores
Bothe, Michael; Orrillo, Alfredo Gastón; Furlan, Ricardo Luis Eugenio; von Delius, Max
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
To expand the toolbox of dynamic covalent and systems chemistry, we investigated the acid-catalyzed exchange reaction of trithioorthoesters with thiols. We found that trithioorthoester exchange occurs readily in various solvents in the presence of stoichiometric amounts of strong Bronsted acids or catalytic amounts of certain Lewis acids. The scope of the exchange reaction was explored with various substrates, and conditions were identified that permit clean metathesis reactions between two different trithioorthoesters. One distinct advantage of S, S, S-orthoester exchange over O, O, O-orthoester exchange is that the exchange reaction can kinetically outcompete hydrolysis, thereby making the process less sensitive to residual moisture. We expect that the relatively high stability of the products might be beneficial in future supramolecular receptors or porous materials.
Fil: Bothe, Michael. Universitat Ulm; Alemania
Fil: Orrillo, Alfredo Gastón. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; Argentina. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Departamento de Química Orgánica. Área Farmacognosia; Argentina
Fil: Furlan, Ricardo Luis Eugenio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; Argentina. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Departamento de Química Orgánica. Área Farmacognosia; Argentina
Fil: von Delius, Max. Universitat Ulm; Alemania
Materia
DYNAMIC COVALENT CHEMISTRY
EXCHANGE A REACTION
METATHESIS
THIOLS
TRANSESTERIFICATION
TRITHIOORTHOESTERS
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/152490
Acceder
id CONICETDig_1dfc34d12860e25d6532ff7413692d93
oai_identifier_str oai:ri.conicet.gov.ar:11336/152490
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Trithioorthoester Exchange and Metathesis: New Tools for Dynamic Covalent ChemistryBothe, MichaelOrrillo, Alfredo GastónFurlan, Ricardo Luis Eugeniovon Delius, MaxDYNAMIC COVALENT CHEMISTRYEXCHANGE A REACTIONMETATHESISTHIOLSTRANSESTERIFICATIONTRITHIOORTHOESTERShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1To expand the toolbox of dynamic covalent and systems chemistry, we investigated the acid-catalyzed exchange reaction of trithioorthoesters with thiols. We found that trithioorthoester exchange occurs readily in various solvents in the presence of stoichiometric amounts of strong Bronsted acids or catalytic amounts of certain Lewis acids. The scope of the exchange reaction was explored with various substrates, and conditions were identified that permit clean metathesis reactions between two different trithioorthoesters. One distinct advantage of S, S, S-orthoester exchange over O, O, O-orthoester exchange is that the exchange reaction can kinetically outcompete hydrolysis, thereby making the process less sensitive to residual moisture. We expect that the relatively high stability of the products might be beneficial in future supramolecular receptors or porous materials.Fil: Bothe, Michael. Universitat Ulm; AlemaniaFil: Orrillo, Alfredo Gastón. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; Argentina. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Departamento de Química Orgánica. Área Farmacognosia; ArgentinaFil: Furlan, Ricardo Luis Eugenio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; Argentina. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Departamento de Química Orgánica. Área Farmacognosia; ArgentinaFil: von Delius, Max. Universitat Ulm; AlemaniaGeorg Thieme Verlag Kg2019-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/152490Bothe, Michael; Orrillo, Alfredo Gastón; Furlan, Ricardo Luis Eugenio; von Delius, Max; Trithioorthoester Exchange and Metathesis: New Tools for Dynamic Covalent Chemistry; Georg Thieme Verlag Kg; Synlett; 30; 17; 9-2019; 1988-19940936-5214CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.thieme-connect.com/products/ejournals/abstract/10.1055/s-0039-1690992info:eu-repo/semantics/altIdentifier/doi/10.1055/s-0039-1690992info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:36:44Zoai:ri.conicet.gov.ar:11336/152490instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:36:44.873CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Trithioorthoester Exchange and Metathesis: New Tools for Dynamic Covalent Chemistry
title Trithioorthoester Exchange and Metathesis: New Tools for Dynamic Covalent Chemistry
spellingShingle Trithioorthoester Exchange and Metathesis: New Tools for Dynamic Covalent Chemistry
Bothe, Michael
DYNAMIC COVALENT CHEMISTRY
EXCHANGE A REACTION
METATHESIS
THIOLS
TRANSESTERIFICATION
TRITHIOORTHOESTERS
title_short Trithioorthoester Exchange and Metathesis: New Tools for Dynamic Covalent Chemistry
title_full Trithioorthoester Exchange and Metathesis: New Tools for Dynamic Covalent Chemistry
title_fullStr Trithioorthoester Exchange and Metathesis: New Tools for Dynamic Covalent Chemistry
title_full_unstemmed Trithioorthoester Exchange and Metathesis: New Tools for Dynamic Covalent Chemistry
title_sort Trithioorthoester Exchange and Metathesis: New Tools for Dynamic Covalent Chemistry
dc.creator.none.fl_str_mv Bothe, Michael
Orrillo, Alfredo Gastón
Furlan, Ricardo Luis Eugenio
von Delius, Max
author Bothe, Michael
author_facet Bothe, Michael
Orrillo, Alfredo Gastón
Furlan, Ricardo Luis Eugenio
von Delius, Max
author_role author
author2 Orrillo, Alfredo Gastón
Furlan, Ricardo Luis Eugenio
von Delius, Max
author2_role author
author
author
dc.subject.none.fl_str_mv DYNAMIC COVALENT CHEMISTRY
EXCHANGE A REACTION
METATHESIS
THIOLS
TRANSESTERIFICATION
TRITHIOORTHOESTERS
topic DYNAMIC COVALENT CHEMISTRY
EXCHANGE A REACTION
METATHESIS
THIOLS
TRANSESTERIFICATION
TRITHIOORTHOESTERS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv To expand the toolbox of dynamic covalent and systems chemistry, we investigated the acid-catalyzed exchange reaction of trithioorthoesters with thiols. We found that trithioorthoester exchange occurs readily in various solvents in the presence of stoichiometric amounts of strong Bronsted acids or catalytic amounts of certain Lewis acids. The scope of the exchange reaction was explored with various substrates, and conditions were identified that permit clean metathesis reactions between two different trithioorthoesters. One distinct advantage of S, S, S-orthoester exchange over O, O, O-orthoester exchange is that the exchange reaction can kinetically outcompete hydrolysis, thereby making the process less sensitive to residual moisture. We expect that the relatively high stability of the products might be beneficial in future supramolecular receptors or porous materials.
Fil: Bothe, Michael. Universitat Ulm; Alemania
Fil: Orrillo, Alfredo Gastón. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; Argentina. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Departamento de Química Orgánica. Área Farmacognosia; Argentina
Fil: Furlan, Ricardo Luis Eugenio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; Argentina. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Departamento de Química Orgánica. Área Farmacognosia; Argentina
Fil: von Delius, Max. Universitat Ulm; Alemania
description To expand the toolbox of dynamic covalent and systems chemistry, we investigated the acid-catalyzed exchange reaction of trithioorthoesters with thiols. We found that trithioorthoester exchange occurs readily in various solvents in the presence of stoichiometric amounts of strong Bronsted acids or catalytic amounts of certain Lewis acids. The scope of the exchange reaction was explored with various substrates, and conditions were identified that permit clean metathesis reactions between two different trithioorthoesters. One distinct advantage of S, S, S-orthoester exchange over O, O, O-orthoester exchange is that the exchange reaction can kinetically outcompete hydrolysis, thereby making the process less sensitive to residual moisture. We expect that the relatively high stability of the products might be beneficial in future supramolecular receptors or porous materials.
publishDate 2019
dc.date.none.fl_str_mv 2019-09
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/152490
Bothe, Michael; Orrillo, Alfredo Gastón; Furlan, Ricardo Luis Eugenio; von Delius, Max; Trithioorthoester Exchange and Metathesis: New Tools for Dynamic Covalent Chemistry; Georg Thieme Verlag Kg; Synlett; 30; 17; 9-2019; 1988-1994
0936-5214
CONICET Digital
CONICET
url http://hdl.handle.net/11336/152490
identifier_str_mv Bothe, Michael; Orrillo, Alfredo Gastón; Furlan, Ricardo Luis Eugenio; von Delius, Max; Trithioorthoester Exchange and Metathesis: New Tools for Dynamic Covalent Chemistry; Georg Thieme Verlag Kg; Synlett; 30; 17; 9-2019; 1988-1994
0936-5214
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.thieme-connect.com/products/ejournals/abstract/10.1055/s-0039-1690992
info:eu-repo/semantics/altIdentifier/doi/10.1055/s-0039-1690992
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Georg Thieme Verlag Kg
publisher.none.fl_str_mv Georg Thieme Verlag Kg
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
_version_ 1844614388121600000
score 13.070432

Publicaciones similares