Osmium-promoted transformation of alkyl nitriles to secondary aliphatic amines: Scope and mechanism

The transformation of alkyl nitriles to symmetrical and asymmetrical secondary aliphatic amines promoted by the hexahydride complex OsH6(PiPr3)2 (1) is described, and the mechanisms of the reactions involved are established. Complex 1 catalyzes the aforementioned transformations of aryl-, pyridyl-,...

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Autores: Babón, Juan C., Esteruelas, Miguel A., López, Ana M., Oñate, Enrique
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2020
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/213756
Acceso en línea:http://hdl.handle.net/10261/213756
Access Level:acceso abierto
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spelling Osmium-promoted transformation of alkyl nitriles to secondary aliphatic amines: Scope and mechanismBabón, Juan C.Esteruelas, Miguel A.López, Ana M.Oñate, EnriqueThe transformation of alkyl nitriles to symmetrical and asymmetrical secondary aliphatic amines promoted by the hexahydride complex OsH6(PiPr3)2 (1) is described, and the mechanisms of the reactions involved are established. Complex 1 catalyzes the aforementioned transformations of aryl-, pyridyl-, and alkoxy-functionalized alkyl nitriles with linear or branched chains. The formation of the secondary amines involves primary imines, primary amines, and secondary imines as organic intermediates. The reactions take place under mild conditions (toluene, 100 °C, and 4 bar of H2). Stoichiometric reactions of 1 with pivalonitrile and 2-methoxyacetonitrile have allowed us to isolate the trihydride azavinylidene derivatives OsH3{═N═CHR}(PiPr3)2 (R = tBu (3), CH2OMe (4)). Their formation involves the insertion of the N–C triple bond of the substrates into an Os–H bond of the unsaturated tetrahydride OsH4(PiPr3)2 (A), which is generated by reductive elimination of H2 from the hexahydride precursor. The reaction of these trihydride azavinylidene species with H2 is the key step for the reduction of the N–C triple bond of the nitriles. In the absence of H2, the attack of A to the azavinylidene ligand produces the rupture of its C(sp2)–C(sp3) bond. As a consequence of this attack and the presence of primary imines and amines in the reaction media, the binuclear complexes (PiPr3)2H4Os(μ-CN)OsH3{κ1-N-(NH═CHCH2OMe)}(PiPr3)2 (5) and (PiPr3)2H4Os(μ-CN)OsH3{κ1-N-(NH2CH2CH2OMe)}(PiPr3)2 (6) have been isolated and characterized by X-ray diffraction analysis, for 2-methoxyacetonitrile. DFT calculations reveal noticeable similarities between the hydrogenations of nitriles to primary imines and those of primary imines to primary amines.Financial support from the MINECO of Spain (Projects CTQ2017-82935-P (AEI/FEDER, UE) and RED2018-102387-T), Gobierno de Aragón (Group E06_20R and project LMP148_18), FEDER, and the European Social Fund is acknowledged.Peer reviewedAmerican Chemical SocietyMinisterio de Ciencia, Innovación y Universidades (España)Gobierno de AragónEuropean CommissionAgencia Estatal de Investigación (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202020202020info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/213756reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/CTQ2017-82935-Pinfo:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RED2018-102387-TCTQ2017-82935-P/AEI/10.13039/501100011033RED2018-102387-T/AEI/10.13039/501100011033https://doi.org/10.1021/acs.organomet.0c00236Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2137562026-05-22T06:33:51Z
dc.title.none.fl_str_mv Osmium-promoted transformation of alkyl nitriles to secondary aliphatic amines: Scope and mechanism
title Osmium-promoted transformation of alkyl nitriles to secondary aliphatic amines: Scope and mechanism
spellingShingle Osmium-promoted transformation of alkyl nitriles to secondary aliphatic amines: Scope and mechanism
Babón, Juan C.
title_short Osmium-promoted transformation of alkyl nitriles to secondary aliphatic amines: Scope and mechanism
title_full Osmium-promoted transformation of alkyl nitriles to secondary aliphatic amines: Scope and mechanism
title_fullStr Osmium-promoted transformation of alkyl nitriles to secondary aliphatic amines: Scope and mechanism
title_full_unstemmed Osmium-promoted transformation of alkyl nitriles to secondary aliphatic amines: Scope and mechanism
title_sort Osmium-promoted transformation of alkyl nitriles to secondary aliphatic amines: Scope and mechanism
dc.creator.none.fl_str_mv Babón, Juan C.
Esteruelas, Miguel A.
López, Ana M.
Oñate, Enrique
author Babón, Juan C.
author_facet Babón, Juan C.
Esteruelas, Miguel A.
López, Ana M.
Oñate, Enrique
author_role author
author2 Esteruelas, Miguel A.
López, Ana M.
Oñate, Enrique
author2_role author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia, Innovación y Universidades (España)
Gobierno de Aragón
European Commission
Agencia Estatal de Investigación (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description The transformation of alkyl nitriles to symmetrical and asymmetrical secondary aliphatic amines promoted by the hexahydride complex OsH6(PiPr3)2 (1) is described, and the mechanisms of the reactions involved are established. Complex 1 catalyzes the aforementioned transformations of aryl-, pyridyl-, and alkoxy-functionalized alkyl nitriles with linear or branched chains. The formation of the secondary amines involves primary imines, primary amines, and secondary imines as organic intermediates. The reactions take place under mild conditions (toluene, 100 °C, and 4 bar of H2). Stoichiometric reactions of 1 with pivalonitrile and 2-methoxyacetonitrile have allowed us to isolate the trihydride azavinylidene derivatives OsH3{═N═CHR}(PiPr3)2 (R = tBu (3), CH2OMe (4)). Their formation involves the insertion of the N–C triple bond of the substrates into an Os–H bond of the unsaturated tetrahydride OsH4(PiPr3)2 (A), which is generated by reductive elimination of H2 from the hexahydride precursor. The reaction of these trihydride azavinylidene species with H2 is the key step for the reduction of the N–C triple bond of the nitriles. In the absence of H2, the attack of A to the azavinylidene ligand produces the rupture of its C(sp2)–C(sp3) bond. As a consequence of this attack and the presence of primary imines and amines in the reaction media, the binuclear complexes (PiPr3)2H4Os(μ-CN)OsH3{κ1-N-(NH═CHCH2OMe)}(PiPr3)2 (5) and (PiPr3)2H4Os(μ-CN)OsH3{κ1-N-(NH2CH2CH2OMe)}(PiPr3)2 (6) have been isolated and characterized by X-ray diffraction analysis, for 2-methoxyacetonitrile. DFT calculations reveal noticeable similarities between the hydrogenations of nitriles to primary imines and those of primary imines to primary amines.
publishDate 2020
dc.date.none.fl_str_mv 2020
2020
2020
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
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status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/213756
url http://hdl.handle.net/10261/213756
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
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info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/CTQ2017-82935-P
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RED2018-102387-T
CTQ2017-82935-P/AEI/10.13039/501100011033
RED2018-102387-T/AEI/10.13039/501100011033
https://doi.org/10.1021/acs.organomet.0c00236
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
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