Sc(OTf)3-catalyzed carbomethoxylation of aliphatic amines with dimethyl carbonate (DMC): DMC activation by η1-O(C=O) coordination to Sc(III) and its relevance to catalysis
The role of metal center in the Sc(OTf)3-catalyzed carbomethoxylation of aliphatic amines with DMC has been investigated. We have shown that the catalytic formation of carbamate ester is promoted by coordination of DMC to scandium(III) ion through the carbonyl oxygen atom. The ability of DMC to coor...
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ftunivbari:oai:ricerca.uniba.it:11586/102512 2024-04-14T08:10:17+00:00 Sc(OTf)3-catalyzed carbomethoxylation of aliphatic amines with dimethyl carbonate (DMC): DMC activation by η1-O(C=O) coordination to Sc(III) and its relevance to catalysis DISTASO M QUARANTA, Eugenio Distaso, M Quaranta, Eugenio 2008 http://hdl.handle.net/11586/102512 https://doi.org/10.1016/j.jcat.2007.11.004 eng eng info:eu-repo/semantics/altIdentifier/wos/000253282000007 volume:253 issue:2 firstpage:278 lastpage:288 numberofpages:11 journal:JOURNAL OF CATALYSIS http://hdl.handle.net/11586/102512 doi:10.1016/j.jcat.2007.11.004 info:eu-repo/semantics/altIdentifier/scopus/2-s2.0-37549047592 amine carbamate dimethyl carbonate homogeneous catalysi transition metal catalyst scandium info:eu-repo/semantics/article 2008 ftunivbari https://doi.org/10.1016/j.jcat.2007.11.004 2024-03-21T18:04:58Z The role of metal center in the Sc(OTf)3-catalyzed carbomethoxylation of aliphatic amines with DMC has been investigated. We have shown that the catalytic formation of carbamate ester is promoted by coordination of DMC to scandium(III) ion through the carbonyl oxygen atom. The ability of DMC to coordinate to Sc(III) has been proved by IR and NMR spectroscopy and fully demonstrated also by the isolation, for the first time, of a DMC–metal complex characterized as (η1-O(C=O)–DMC)Sc(OTf)3. A relationship has been shown between the coordination mode of DMC to Sc(III) and the reactivity of coordinated organic carbonate: coordination of DMC to Sc(III) activates both carbonyl group and O–CH3 moieties of the carbonic acid diester and enhances not only the carbomethoxylating but also the methylating activity of the ambident electrophile (DMC), as documented by the different selectivity exhibited by the catalyst in the aminolysis reaction of DMC with benzylamine and aniline, respectively. Article in Journal/Newspaper Carbonic acid Università degli Studi di Bari Aldo Moro: CINECA IRIS Journal of Catalysis 253 2 278 288 |
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Open Polar |
collection |
Università degli Studi di Bari Aldo Moro: CINECA IRIS |
op_collection_id |
ftunivbari |
language |
English |
topic |
amine carbamate dimethyl carbonate homogeneous catalysi transition metal catalyst scandium |
spellingShingle |
amine carbamate dimethyl carbonate homogeneous catalysi transition metal catalyst scandium DISTASO M QUARANTA, Eugenio Sc(OTf)3-catalyzed carbomethoxylation of aliphatic amines with dimethyl carbonate (DMC): DMC activation by η1-O(C=O) coordination to Sc(III) and its relevance to catalysis |
topic_facet |
amine carbamate dimethyl carbonate homogeneous catalysi transition metal catalyst scandium |
description |
The role of metal center in the Sc(OTf)3-catalyzed carbomethoxylation of aliphatic amines with DMC has been investigated. We have shown that the catalytic formation of carbamate ester is promoted by coordination of DMC to scandium(III) ion through the carbonyl oxygen atom. The ability of DMC to coordinate to Sc(III) has been proved by IR and NMR spectroscopy and fully demonstrated also by the isolation, for the first time, of a DMC–metal complex characterized as (η1-O(C=O)–DMC)Sc(OTf)3. A relationship has been shown between the coordination mode of DMC to Sc(III) and the reactivity of coordinated organic carbonate: coordination of DMC to Sc(III) activates both carbonyl group and O–CH3 moieties of the carbonic acid diester and enhances not only the carbomethoxylating but also the methylating activity of the ambident electrophile (DMC), as documented by the different selectivity exhibited by the catalyst in the aminolysis reaction of DMC with benzylamine and aniline, respectively. |
author2 |
Distaso, M Quaranta, Eugenio |
format |
Article in Journal/Newspaper |
author |
DISTASO M QUARANTA, Eugenio |
author_facet |
DISTASO M QUARANTA, Eugenio |
author_sort |
DISTASO M |
title |
Sc(OTf)3-catalyzed carbomethoxylation of aliphatic amines with dimethyl carbonate (DMC): DMC activation by η1-O(C=O) coordination to Sc(III) and its relevance to catalysis |
title_short |
Sc(OTf)3-catalyzed carbomethoxylation of aliphatic amines with dimethyl carbonate (DMC): DMC activation by η1-O(C=O) coordination to Sc(III) and its relevance to catalysis |
title_full |
Sc(OTf)3-catalyzed carbomethoxylation of aliphatic amines with dimethyl carbonate (DMC): DMC activation by η1-O(C=O) coordination to Sc(III) and its relevance to catalysis |
title_fullStr |
Sc(OTf)3-catalyzed carbomethoxylation of aliphatic amines with dimethyl carbonate (DMC): DMC activation by η1-O(C=O) coordination to Sc(III) and its relevance to catalysis |
title_full_unstemmed |
Sc(OTf)3-catalyzed carbomethoxylation of aliphatic amines with dimethyl carbonate (DMC): DMC activation by η1-O(C=O) coordination to Sc(III) and its relevance to catalysis |
title_sort |
sc(otf)3-catalyzed carbomethoxylation of aliphatic amines with dimethyl carbonate (dmc): dmc activation by η1-o(c=o) coordination to sc(iii) and its relevance to catalysis |
publishDate |
2008 |
url |
http://hdl.handle.net/11586/102512 https://doi.org/10.1016/j.jcat.2007.11.004 |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_relation |
info:eu-repo/semantics/altIdentifier/wos/000253282000007 volume:253 issue:2 firstpage:278 lastpage:288 numberofpages:11 journal:JOURNAL OF CATALYSIS http://hdl.handle.net/11586/102512 doi:10.1016/j.jcat.2007.11.004 info:eu-repo/semantics/altIdentifier/scopus/2-s2.0-37549047592 |
op_doi |
https://doi.org/10.1016/j.jcat.2007.11.004 |
container_title |
Journal of Catalysis |
container_volume |
253 |
container_issue |
2 |
container_start_page |
278 |
op_container_end_page |
288 |
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1796307812242948096 |