Towards a general ruthenium-catalyzed hydrogenation of secondary and tertiary amides to amines
A broad range of secondary and tertiary amides has been hydrogenated to the corresponding amines under mild conditions using an in situ catalyst generated by combining [Ru(acac) 3 ], 1,1,1-tris(diphenylphosphinomethyl)ethane (Triphos) and Yb(OTf) 3 . The presence of the metal triflate allows to miti...
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| Veröffentlicht in: | Chemical science (Cambridge) 2016-01, Vol.7 (5), p.3432-3442 |
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| creator | Cabrero-Antonino, Jose R Alberico, Elisabetta Junge, Kathrin Junge, Henrik Beller, Matthias |
| description | A broad range of secondary and tertiary amides has been hydrogenated to the corresponding amines under mild conditions using an
in situ
catalyst generated by combining [Ru(acac)
3
], 1,1,1-tris(diphenylphosphinomethyl)ethane (Triphos) and Yb(OTf)
3
. The presence of the metal triflate allows to mitigate reaction conditions compared to previous reports thus improving yields and selectivities in the desired amines. The excellent isolated yields of two scale-up experiments corroborate the feasibility of the reaction protocol. Control experiments indicate that, after the initial reduction of the amide carbonyl group, the reaction proceeds through the reductive amination of the alcohol with the amine arising from collapse of the intermediate hemiaminal.
[Ru(acac)
3
]/Triphos in combination with Yb(OTf)
3
constitutes an improved catalyst system for the hydrogenation of aliphatic and aromatic secondary and tertiary amides. |
| doi_str_mv | 10.1039/c5sc04671h |
| format | Article |
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in situ
catalyst generated by combining [Ru(acac)
3
], 1,1,1-tris(diphenylphosphinomethyl)ethane (Triphos) and Yb(OTf)
3
. The presence of the metal triflate allows to mitigate reaction conditions compared to previous reports thus improving yields and selectivities in the desired amines. The excellent isolated yields of two scale-up experiments corroborate the feasibility of the reaction protocol. Control experiments indicate that, after the initial reduction of the amide carbonyl group, the reaction proceeds through the reductive amination of the alcohol with the amine arising from collapse of the intermediate hemiaminal.
[Ru(acac)
3
]/Triphos in combination with Yb(OTf)
3
constitutes an improved catalyst system for the hydrogenation of aliphatic and aromatic secondary and tertiary amides.</description><identifier>ISSN: 2041-6520</identifier><identifier>EISSN: 2041-6539</identifier><identifier>DOI: 10.1039/c5sc04671h</identifier><identifier>PMID: 29997838</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Amides ; Amines ; Carbonyl groups ; Chemistry ; Collapse ; Feasibility ; Hydrogenation ; Reduction ; Selectivity</subject><ispartof>Chemical science (Cambridge), 2016-01, Vol.7 (5), p.3432-3442</ispartof><rights>This journal is © The Royal Society of Chemistry 2016 2016</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c499t-323375d93b2c8bcd0c8f9245242950741e483a8cd16f6c1a1cc7f96de47682ed3</citedby><cites>FETCH-LOGICAL-c499t-323375d93b2c8bcd0c8f9245242950741e483a8cd16f6c1a1cc7f96de47682ed3</cites><orcidid>0000-0002-1143-6032 ; 0000-0001-7044-8888 ; 0000-0002-7603-1984 ; 0000-0001-9628-9803</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC6006866/pdf/$$EPDF$$P50$$Gpubmedcentral$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC6006866/$$EHTML$$P50$$Gpubmedcentral$$Hfree_for_read</linktohtml><link.rule.ids>230,314,725,778,782,862,883,27907,27908,53774,53776</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/29997838$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Cabrero-Antonino, Jose R</creatorcontrib><creatorcontrib>Alberico, Elisabetta</creatorcontrib><creatorcontrib>Junge, Kathrin</creatorcontrib><creatorcontrib>Junge, Henrik</creatorcontrib><creatorcontrib>Beller, Matthias</creatorcontrib><title>Towards a general ruthenium-catalyzed hydrogenation of secondary and tertiary amides to amines</title><title>Chemical science (Cambridge)</title><addtitle>Chem Sci</addtitle><description>A broad range of secondary and tertiary amides has been hydrogenated to the corresponding amines under mild conditions using an
in situ
catalyst generated by combining [Ru(acac)
3
], 1,1,1-tris(diphenylphosphinomethyl)ethane (Triphos) and Yb(OTf)
3
. The presence of the metal triflate allows to mitigate reaction conditions compared to previous reports thus improving yields and selectivities in the desired amines. The excellent isolated yields of two scale-up experiments corroborate the feasibility of the reaction protocol. Control experiments indicate that, after the initial reduction of the amide carbonyl group, the reaction proceeds through the reductive amination of the alcohol with the amine arising from collapse of the intermediate hemiaminal.
[Ru(acac)
3
]/Triphos in combination with Yb(OTf)
3
constitutes an improved catalyst system for the hydrogenation of aliphatic and aromatic secondary and tertiary amides.</description><subject>Amides</subject><subject>Amines</subject><subject>Carbonyl groups</subject><subject>Chemistry</subject><subject>Collapse</subject><subject>Feasibility</subject><subject>Hydrogenation</subject><subject>Reduction</subject><subject>Selectivity</subject><issn>2041-6520</issn><issn>2041-6539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><recordid>eNqFkc1rVTEQxYMottRu3CtZinBtvm4-NoI8rBUKXbRuDXnJ3L4r9yY1ya08__qmffWpq85mZpgfhzMchF5T8oESbk58XzwRUtHNM3TIiKCd7Ll5vp8ZOUDHpfwgrTinPVMv0QEzxijN9SH6fpV-uRwKdvgaImQ34bzUDcRxmTvvqpu2vyHgzTbk1ABXxxRxGnABn2JweYtdDLhCruPDMo8BCq7pfopQXqEXg5sKHD_2I_Tt9PPV6qw7v_jydfXpvPPCmNpxxrnqg-Fr5vXaB-L1YJjomWCmJ0pQEJo77QOVg_TUUe_VYGQAoaRmEPgR-rjTvVnWMwQPsbZX7E0e52bLJjfa_y9x3NjrdGslIVJL2QTePQrk9HOBUu08Fg_T5CKkpVjWsOaIKvokSjXRpNfKiIa-36E-p1IyDHtHlNj7-Oyqv1w9xHfW4Lf__rBH_4TVgDc7IBe_v_7Nn98BQQeg5A</recordid><startdate>20160101</startdate><enddate>20160101</enddate><creator>Cabrero-Antonino, Jose R</creator><creator>Alberico, Elisabetta</creator><creator>Junge, Kathrin</creator><creator>Junge, Henrik</creator><creator>Beller, Matthias</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0002-1143-6032</orcidid><orcidid>https://orcid.org/0000-0001-7044-8888</orcidid><orcidid>https://orcid.org/0000-0002-7603-1984</orcidid><orcidid>https://orcid.org/0000-0001-9628-9803</orcidid></search><sort><creationdate>20160101</creationdate><title>Towards a general ruthenium-catalyzed hydrogenation of secondary and tertiary amides to amines</title><author>Cabrero-Antonino, Jose R ; Alberico, Elisabetta ; Junge, Kathrin ; Junge, Henrik ; Beller, Matthias</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c499t-323375d93b2c8bcd0c8f9245242950741e483a8cd16f6c1a1cc7f96de47682ed3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2016</creationdate><topic>Amides</topic><topic>Amines</topic><topic>Carbonyl groups</topic><topic>Chemistry</topic><topic>Collapse</topic><topic>Feasibility</topic><topic>Hydrogenation</topic><topic>Reduction</topic><topic>Selectivity</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Cabrero-Antonino, Jose R</creatorcontrib><creatorcontrib>Alberico, Elisabetta</creatorcontrib><creatorcontrib>Junge, Kathrin</creatorcontrib><creatorcontrib>Junge, Henrik</creatorcontrib><creatorcontrib>Beller, Matthias</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Chemical science (Cambridge)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Cabrero-Antonino, Jose R</au><au>Alberico, Elisabetta</au><au>Junge, Kathrin</au><au>Junge, Henrik</au><au>Beller, Matthias</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Towards a general ruthenium-catalyzed hydrogenation of secondary and tertiary amides to amines</atitle><jtitle>Chemical science (Cambridge)</jtitle><addtitle>Chem Sci</addtitle><date>2016-01-01</date><risdate>2016</risdate><volume>7</volume><issue>5</issue><spage>3432</spage><epage>3442</epage><pages>3432-3442</pages><issn>2041-6520</issn><eissn>2041-6539</eissn><abstract>A broad range of secondary and tertiary amides has been hydrogenated to the corresponding amines under mild conditions using an
in situ
catalyst generated by combining [Ru(acac)
3
], 1,1,1-tris(diphenylphosphinomethyl)ethane (Triphos) and Yb(OTf)
3
. The presence of the metal triflate allows to mitigate reaction conditions compared to previous reports thus improving yields and selectivities in the desired amines. The excellent isolated yields of two scale-up experiments corroborate the feasibility of the reaction protocol. Control experiments indicate that, after the initial reduction of the amide carbonyl group, the reaction proceeds through the reductive amination of the alcohol with the amine arising from collapse of the intermediate hemiaminal.
[Ru(acac)
3
]/Triphos in combination with Yb(OTf)
3
constitutes an improved catalyst system for the hydrogenation of aliphatic and aromatic secondary and tertiary amides.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>29997838</pmid><doi>10.1039/c5sc04671h</doi><tpages>11</tpages><orcidid>https://orcid.org/0000-0002-1143-6032</orcidid><orcidid>https://orcid.org/0000-0001-7044-8888</orcidid><orcidid>https://orcid.org/0000-0002-7603-1984</orcidid><orcidid>https://orcid.org/0000-0001-9628-9803</orcidid><oa>free_for_read</oa></addata></record> |
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| language | eng |
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| source | DOAJ Directory of Open Access Journals; PubMed Central Open Access; EZB-FREE-00999 freely available EZB journals; PubMed Central |
| subjects | Amides Amines Carbonyl groups Chemistry Collapse Feasibility Hydrogenation Reduction Selectivity |
| title | Towards a general ruthenium-catalyzed hydrogenation of secondary and tertiary amides to amines |
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