Ligand-to-metal ratio controls stereoselectivity: Highly functional-group-tolerant, iridium-based, (E)-selective alkyne transfer semihydrogenation

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dc.contributor.authorKusy, Rafał
dc.contributor.authorLindner, Marcin
dc.contributor.authorWagner, Jakub
dc.contributor.authorGrela, Karol
dc.contributor.organizationInstitute of Organic Chemistry, Polish Academy of Sciencesen
dc.date.accessioned2022-08-31T13:21:26Z
dc.date.available2022-08-31T13:21:26Z
dc.date.issued2022
dc.description.abstractHerein, we present (E)-selective transfer semihydrogenation of al kynes based on an iridium complex in situ generated from [Ir(COD)Cl]2 and an unsymmetrical (bearing two different phosphorous cen ters), ferrocene-based phosphine ligand utilizing formic acid as a hydrogen donor. Interestingly, a ligand-to-metal ratio may be used to control the stereoselectivity of the semihydrogenation pro cess: a ratio of 1:1 iridium to ligand led to the formation of (Z)-alkene as a major product, whereas a ratio of 1:2 gave exclusively (E)-alkene. The latter 1:2 catalytic system is distinguished by its unprec edented chemoselectivity and exceptional stereoselectivity, which is substantiated by the broad scope of tested substrates, including natural product derivatives. The intriguing difference in catalytic ac tivity between unsymmetrical and symmetrical ferrocene-based li gands was attributed to divergent coordination and steric hin drance. The presented methodology constitutes a solution to the common limitations of the known catalytic systems for semihydro genation.en
dc.description.sponsorshipNational Science Centre, OPUS grant no. UMO-2017/25/B/ST5/01274
dc.identifier.citationKusy et al., Chem Catalysis 2, 1346—1361 June 16, 2022. https://doi.org/10.1016/j.checat.2022.04.014en
dc.identifier.doi10.1016/j.checat.2022.04.014
dc.identifier.issn2667-1093
dc.identifier.urihttps://open.icm.edu.pl/handle/123456789/21595
dc.language.isoen
dc.publisherElsevieren
dc.rightsAttribution-NonCommercial-NoDerivatives 4.0 Międzynarodowe*
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/*
dc.subjectsemihydrogenationen
dc.subjectalkynesen
dc.subjectalkenesen
dc.subjectiridiumen
dc.subjecthomogeneous catalysisen
dc.titleLigand-to-metal ratio controls stereoselectivity: Highly functional-group-tolerant, iridium-based, (E)-selective alkyne transfer semihydrogenationen
dc.typearticleen
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