Radical and Ionic Mechanisms in Rearrangements of o-Tolyl Aryl Ethers and Amines Initiated by the Grubbs–Stoltz Reagent, Et3SiH/KOtBu

Rearrangements of o-tolyl aryl ethers, amines, and sulfides with the Grubbs–Stoltz reagent (Et3SiH + KOtBu) were recently announced, in which the ethers were converted to o-hydroxydiarylmethanes, w...

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Autores principales:	Krystian Kolodziejczak, Alexander J. Stewart, Tell Tuttle, John A. Murphy
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	Truce–Smiles rearrangement Grubbs–Stoltz reagent radical electron transfer aryl substitution diarylmethanes Organic chemistry QD241-441
Acceso en línea:	https://doaj.org/article/03077899a6ae4b57a6121c3f428c75da
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spelling	oai:doaj.org-article:03077899a6ae4b57a6121c3f428c75da2021-11-25T18:28:03ZRadical and Ionic Mechanisms in Rearrangements of <i>o</i>-Tolyl Aryl Ethers and Amines Initiated by the Grubbs–Stoltz Reagent, Et<sub>3</sub>SiH/KO<i><sup>t</sup></i>Bu10.3390/molecules262268791420-3049https://doaj.org/article/03077899a6ae4b57a6121c3f428c75da2021-11-01T00:00:00Zhttps://www.mdpi.com/1420-3049/26/22/6879https://doaj.org/toc/1420-3049Rearrangements of <i>o-</i>tolyl aryl ethers, amines, and sulfides with the Grubbs–Stoltz reagent (Et<sub>3</sub>SiH + KO<i><sup>t</sup></i>Bu) were recently announced, in which the ethers were converted to <i>o</i>-hydroxydiarylmethanes, while the (<i>o-</i>tol)(Ar)NH amines were transformed into dihydroacridines. Radical mechanisms were proposed, based on prior evidence for triethylsilyl radicals in this reagent system. A detailed computational investigation of the rearrangements of the aryl tolyl ethers now instead supports an anionic Truce–Smiles rearrangement, where the initial benzyl anion can be formed by either of two pathways: (i) direct deprotonation of the tolyl methyl group under basic conditions or (ii) electron transfer to an initially formed benzyl radical. By contrast, the rearrangements of <i>o-</i>tolyl aryl amines depend on the nature of the amine. Secondary amines undergo deprotonation of the N-H followed by a radical rearrangement, to form dihydroacridines, while tertiary amines form both dihydroacridines and diarylmethanes through radical and/or anionic pathways. Overall, this study highlights the competition between the reactive intermediates formed by the Et<sub>3</sub>SiH/KO<i><sup>t</sup></i>Bu system.Krystian KolodziejczakAlexander J. StewartTell TuttleJohn A. MurphyMDPI AGarticleTruce–Smiles rearrangementGrubbs–Stoltz reagentradicalelectron transferaryl substitutiondiarylmethanesOrganic chemistryQD241-441ENMolecules, Vol 26, Iss 6879, p 6879 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	Truce–Smiles rearrangement Grubbs–Stoltz reagent radical electron transfer aryl substitution diarylmethanes Organic chemistry QD241-441
spellingShingle	Truce–Smiles rearrangement Grubbs–Stoltz reagent radical electron transfer aryl substitution diarylmethanes Organic chemistry QD241-441 Krystian Kolodziejczak Alexander J. Stewart Tell Tuttle John A. Murphy Radical and Ionic Mechanisms in Rearrangements of <i>o</i>-Tolyl Aryl Ethers and Amines Initiated by the Grubbs–Stoltz Reagent, Et<sub>3</sub>SiH/KO<i><sup>t</sup></i>Bu
description	Rearrangements of <i>o-</i>tolyl aryl ethers, amines, and sulfides with the Grubbs–Stoltz reagent (Et<sub>3</sub>SiH + KO<i><sup>t</sup></i>Bu) were recently announced, in which the ethers were converted to <i>o</i>-hydroxydiarylmethanes, while the (<i>o-</i>tol)(Ar)NH amines were transformed into dihydroacridines. Radical mechanisms were proposed, based on prior evidence for triethylsilyl radicals in this reagent system. A detailed computational investigation of the rearrangements of the aryl tolyl ethers now instead supports an anionic Truce–Smiles rearrangement, where the initial benzyl anion can be formed by either of two pathways: (i) direct deprotonation of the tolyl methyl group under basic conditions or (ii) electron transfer to an initially formed benzyl radical. By contrast, the rearrangements of <i>o-</i>tolyl aryl amines depend on the nature of the amine. Secondary amines undergo deprotonation of the N-H followed by a radical rearrangement, to form dihydroacridines, while tertiary amines form both dihydroacridines and diarylmethanes through radical and/or anionic pathways. Overall, this study highlights the competition between the reactive intermediates formed by the Et<sub>3</sub>SiH/KO<i><sup>t</sup></i>Bu system.
format	article
author	Krystian Kolodziejczak Alexander J. Stewart Tell Tuttle John A. Murphy
author_facet	Krystian Kolodziejczak Alexander J. Stewart Tell Tuttle John A. Murphy
author_sort	Krystian Kolodziejczak
title	Radical and Ionic Mechanisms in Rearrangements of <i>o</i>-Tolyl Aryl Ethers and Amines Initiated by the Grubbs–Stoltz Reagent, Et<sub>3</sub>SiH/KO<i><sup>t</sup></i>Bu
title_short	Radical and Ionic Mechanisms in Rearrangements of <i>o</i>-Tolyl Aryl Ethers and Amines Initiated by the Grubbs–Stoltz Reagent, Et<sub>3</sub>SiH/KO<i><sup>t</sup></i>Bu
title_full	Radical and Ionic Mechanisms in Rearrangements of <i>o</i>-Tolyl Aryl Ethers and Amines Initiated by the Grubbs–Stoltz Reagent, Et<sub>3</sub>SiH/KO<i><sup>t</sup></i>Bu
title_fullStr	Radical and Ionic Mechanisms in Rearrangements of <i>o</i>-Tolyl Aryl Ethers and Amines Initiated by the Grubbs–Stoltz Reagent, Et<sub>3</sub>SiH/KO<i><sup>t</sup></i>Bu
title_full_unstemmed	Radical and Ionic Mechanisms in Rearrangements of <i>o</i>-Tolyl Aryl Ethers and Amines Initiated by the Grubbs–Stoltz Reagent, Et<sub>3</sub>SiH/KO<i><sup>t</sup></i>Bu
title_sort	radical and ionic mechanisms in rearrangements of <i>o</i>-tolyl aryl ethers and amines initiated by the grubbs–stoltz reagent, et<sub>3</sub>sih/ko<i><sup>t</sup></i>bu
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/03077899a6ae4b57a6121c3f428c75da
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_version_	1718411115114790912

Radical and Ionic Mechanisms in Rearrangements of <i>o</i>-Tolyl Aryl Ethers and Amines Initiated by the Grubbs–Stoltz Reagent, Et<sub>3</sub>SiH/KO<i><sup>t</sup></i>Bu

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