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A photochemical dehydrogenative strategy for aniline synthesis

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dc.contributor.authorDighe, Shashikant
dc.contributor.authorJuliá Hernández, Fabio
dc.contributor.authorLuridiana, Alberto
dc.contributor.authorDouglas, James J.
dc.contributor.authorLeonori, Daniele
dc.contributor.departmentQuímica Inorgánica
dc.date.accessioned2025-01-24T11:31:27Z
dc.date.available2025-01-24T11:31:27Z
dc.date.issued2020-08-06
dc.description© 2020, The Author(s), under exclusive licence to Springer Nature Limited. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ This document is the Accepted Manuscript version of a Published Work that appeared in final form in Nature. To access the final edited and published work see https://doi.org/10.1038/s41586-020-2539-7
dc.description.abstractChemical reactions that reliably join two molecular fragments together (cross-couplings) are essential to the discovery and manufacture of pharmaceuticals and agrochemicals1,2. The introduction of amines onto functionalized aromatics at specific and pre-determined positions (ortho versus meta versus para) is currently achievable only in transition-metal-catalysed processes and requires halogen- or boron-containing substrates3,4,5,6. The introduction of these groups around the aromatic unit is dictated by the intrinsic reactivity profile of the method (electrophilic halogenation or C–H borylation) so selective targeting of all positions is often not possible. Here we report a non-canonical cross-coupling approach for the construction of anilines, exploiting saturated cyclohexanones as aryl electrophile surrogates. Condensation between amines and carbonyls, a process that frequently occurs in nature and is often used by (bio-)organic chemists7, enables a predetermined and site-selective carbon–nitrogen (C–N) bond formation, while a photoredox- and cobalt-based catalytic system progressively desaturates the cyclohexene ring en route to the aniline. Given that functionalized cyclohexanones are readily accessible with complete regiocontrol using the well established carbonyl reactivity, this approach bypasses some of the frequent selectivity issues of aromatic chemistry. We demonstrate the utility of this C–N coupling protocol by preparing commercial medicines and by the late-stage amination–aromatization of natural products, steroids and terpene feedstocks.
dc.formatapplication/pdfes
dc.format.extent15
dc.identifier.citationNature, 2020, Vol. 584, pp. 75-81
dc.identifier.doihttps://doi.org/10.1038/s41586-020-2539-7
dc.identifier.issnPrint: 0028-0836
dc.identifier.issnElectronic: 1476-4687
dc.identifier.urihttp://hdl.handle.net/10201/149267
dc.languageenges
dc.publisherNature Research
dc.relationD. L. thanks EPSRC for a Fellowship (EP/P004997/1) and the European Research Council for a research grant (758427). S.D. thanks the Marie Curie Actions for a Fellowship (791349).es
dc.relation.publisherversionhttps://www.nature.com/articles/s41586-020-2539-7
dc.rightsinfo:eu-repo/semantics/openAccesses
dc.rightsAttribution-NonCommercial-NoDerivatives 4.0 Internacional*
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/*
dc.subjectSynthetic chemistry methodology
dc.subjectPhotocatalysis
dc.titleA photochemical dehydrogenative strategy for aniline synthesises
dc.typeinfo:eu-repo/semantics/articlees
dspace.entity.typePublicationes
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