Titanium(III)‐Catalyzed Reductive Decyanation of Geminal Dinitriles by a Non‐Free‐Radical Mechanism

A titanium‐catalyzed mono‐decyanation of geminal dinitriles is reported. The reaction proceeds under mild conditions, tolerates numerous functional groups, and can be applied to quaternary malononitriles. A corresponding desulfonylation is demonstrated as well. Mechanistic experiments support a cata...

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Autores principales: Weweler, Jens, Younas, Sara L., Streuff, Jan
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2019
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6899653/
https://www.ncbi.nlm.nih.gov/pubmed/31513329
http://dx.doi.org/10.1002/anie.201908372
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author Weweler, Jens
Younas, Sara L.
Streuff, Jan
author_facet Weweler, Jens
Younas, Sara L.
Streuff, Jan
author_sort Weweler, Jens
collection PubMed
description A titanium‐catalyzed mono‐decyanation of geminal dinitriles is reported. The reaction proceeds under mild conditions, tolerates numerous functional groups, and can be applied to quaternary malononitriles. A corresponding desulfonylation is demonstrated as well. Mechanistic experiments support a catalyst‐controlled cleavage without the formation of free radicals, which is in sharp contrast to traditional stoichiometric radical decyanations. The involvement of two Ti(III) species in the C−C cleavage is proposed, and the beneficial role of added ZnCl(2) and 2,4,6‐collidine hydrochloride is investigated.
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spelling pubmed-68996532019-12-19 Titanium(III)‐Catalyzed Reductive Decyanation of Geminal Dinitriles by a Non‐Free‐Radical Mechanism Weweler, Jens Younas, Sara L. Streuff, Jan Angew Chem Int Ed Engl Communications A titanium‐catalyzed mono‐decyanation of geminal dinitriles is reported. The reaction proceeds under mild conditions, tolerates numerous functional groups, and can be applied to quaternary malononitriles. A corresponding desulfonylation is demonstrated as well. Mechanistic experiments support a catalyst‐controlled cleavage without the formation of free radicals, which is in sharp contrast to traditional stoichiometric radical decyanations. The involvement of two Ti(III) species in the C−C cleavage is proposed, and the beneficial role of added ZnCl(2) and 2,4,6‐collidine hydrochloride is investigated. John Wiley and Sons Inc. 2019-10-23 2019-12-02 /pmc/articles/PMC6899653/ /pubmed/31513329 http://dx.doi.org/10.1002/anie.201908372 Text en © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Communications
Weweler, Jens
Younas, Sara L.
Streuff, Jan
Titanium(III)‐Catalyzed Reductive Decyanation of Geminal Dinitriles by a Non‐Free‐Radical Mechanism
title Titanium(III)‐Catalyzed Reductive Decyanation of Geminal Dinitriles by a Non‐Free‐Radical Mechanism
title_full Titanium(III)‐Catalyzed Reductive Decyanation of Geminal Dinitriles by a Non‐Free‐Radical Mechanism
title_fullStr Titanium(III)‐Catalyzed Reductive Decyanation of Geminal Dinitriles by a Non‐Free‐Radical Mechanism
title_full_unstemmed Titanium(III)‐Catalyzed Reductive Decyanation of Geminal Dinitriles by a Non‐Free‐Radical Mechanism
title_short Titanium(III)‐Catalyzed Reductive Decyanation of Geminal Dinitriles by a Non‐Free‐Radical Mechanism
title_sort titanium(iii)‐catalyzed reductive decyanation of geminal dinitriles by a non‐free‐radical mechanism
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6899653/
https://www.ncbi.nlm.nih.gov/pubmed/31513329
http://dx.doi.org/10.1002/anie.201908372
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AT streuffjan titaniumiiicatalyzedreductivedecyanationofgeminaldinitrilesbyanonfreeradicalmechanism

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