KOPS - The Institutional Repository of the University of Konstanz

Catalytic Regioselective Benzoylation of 1,2-trans-Diols in Carbohydrates with Benzoyl Cyanide : The Axial Oxy Group Effect and the Action of Achiral and Chiral Amine Catalysts

Catalytic Regioselective Benzoylation of 1,2-trans-Diols in Carbohydrates with Benzoyl Cyanide : The Axial Oxy Group Effect and the Action of Achiral and Chiral Amine Catalysts

Cite This

Files in this item

Files Size Format View

There are no files associated with this item.

LI, Tianlu, Tong LI, Michael LINSEIS, Fengshan WANG, Rainer F. WINTER, Richard R. SCHMIDT, Peng PENG, 2020. Catalytic Regioselective Benzoylation of 1,2-trans-Diols in Carbohydrates with Benzoyl Cyanide : The Axial Oxy Group Effect and the Action of Achiral and Chiral Amine Catalysts. In: ACS Catalysis. ACS Publications. 10(19), pp. 11406-11416. eISSN 2155-5435. Available under: doi: 10.1021/acscatal.0c02112

@article{Li2020-10-02Catal-51320, title={Catalytic Regioselective Benzoylation of 1,2-trans-Diols in Carbohydrates with Benzoyl Cyanide : The Axial Oxy Group Effect and the Action of Achiral and Chiral Amine Catalysts}, year={2020}, doi={10.1021/acscatal.0c02112}, number={19}, volume={10}, journal={ACS Catalysis}, pages={11406--11416}, author={Li, Tianlu and Li, Tong and Linseis, Michael and Wang, Fengshan and Winter, Rainer F. and Schmidt, Richard R. and Peng, Peng} }

<rdf:RDF xmlns:dcterms="http://purl.org/dc/terms/" xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#" xmlns:bibo="http://purl.org/ontology/bibo/" xmlns:dspace="http://digital-repositories.org/ontologies/dspace/0.1.0#" xmlns:foaf="http://xmlns.com/foaf/0.1/" xmlns:void="http://rdfs.org/ns/void#" xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > <rdf:Description rdf:about="https://kops.uni-konstanz.de/rdf/resource/123456789/51320"> <dc:contributor>Wang, Fengshan</dc:contributor> <dc:contributor>Li, Tong</dc:contributor> <dc:rights>terms-of-use</dc:rights> <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/29"/> <dc:creator>Linseis, Michael</dc:creator> <dc:contributor>Peng, Peng</dc:contributor> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2020-10-13T11:02:27Z</dcterms:available> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2020-10-13T11:02:27Z</dc:date> <dcterms:issued>2020-10-02</dcterms:issued> <dc:creator>Peng, Peng</dc:creator> <dc:creator>Li, Tianlu</dc:creator> <dc:language>eng</dc:language> <dc:contributor>Schmidt, Richard R.</dc:contributor> <dc:contributor>Winter, Rainer F.</dc:contributor> <dc:creator>Winter, Rainer F.</dc:creator> <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/29"/> <dc:creator>Li, Tong</dc:creator> <foaf:homepage rdf:resource="http://localhost:8080/jspui"/> <dcterms:rights rdf:resource="https://rightsstatements.org/page/InC/1.0/"/> <dc:creator>Schmidt, Richard R.</dc:creator> <dcterms:title>Catalytic Regioselective Benzoylation of 1,2-trans-Diols in Carbohydrates with Benzoyl Cyanide : The Axial Oxy Group Effect and the Action of Achiral and Chiral Amine Catalysts</dcterms:title> <dc:creator>Wang, Fengshan</dc:creator> <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/> <dc:contributor>Li, Tianlu</dc:contributor> <dcterms:abstract xml:lang="eng">Regioselective protection of the polyfunctional carbohydrates with acyl groups under catalytic conditions is a prerequisite for efficient structural modification and chain extension via glycosidation. A general and also strong “axial oxy group effect” was now observed with benzoyl cyanide as the acylating agent and 4-dimethylaminopyridine as the catalyst, permitting the preferred O-acylation of equatorial hydroxy groups next to axial oxy groups. This effect is substantiated with 2,3-O-unprotected β-d-galacto- and α-d-glucopyranosides and 3,4-O-unprotected mannopyranosides possessing vicinal trans-diol moieties. Moreover, vicinal trans-diols with axial oxy groups next to each hydroxy group, possessing expectedly comparable reactivity, could be differentiated with chiral tertiary amine catalysts. Particularly interesting in this regard is the action of bifunctional (S,S)-N-(N,N-dialkylaminocyclohexyl)-thioureas as catalysts; they favor 2-O-benzoylation of 2,3-O-unprotected α-galactopyranosides, as is also supported by density functional theory calculations. This directing effect can be reversed with quinidine as the catalyst or with bulky substituents at the anomeric position.</dcterms:abstract> <bibo:uri rdf:resource="https://kops.uni-konstanz.de/handle/123456789/51320"/> <dc:contributor>Linseis, Michael</dc:contributor> </rdf:Description> </rdf:RDF>

This item appears in the following Collection(s)

Search KOPS


Browse

My Account