Acid-Catalyzed Solvent-Switchable Chemoselective N-Alkylation and para C-Alkylation of Unprotected Arylamines Utilizing ortho-Quinone Methides

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 21, 2025

Nitrogen-containing compounds, such as anilines, represent some of the most prevalent and valuable chemical entities within field chemistry. However, their high reactivity, which frequently lacks selectivity, has constrained application in various transformations, including alkylation alcohols. In present study, we successfully accomplished site-selective para N-H anilines by utilizing ortho-quinone methides under mild conditions. The regioselective para-alkylation was conducted with unprotected a metal-free environment, while alkylations were effectively performed similarly DFT calculations carried out to understand distinctive chemoselectivity N-alkylation C-alkylation arylamines different nonpolar (toluene) polar protic (HFIP) solvents. Furthermore, transition state models identified our shed light on intricate interplay between solvent effects reaction selectivity.

Язык: Английский

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1,1,1,3,3,3-Hexafluoro-2-propanol (HFIP)-promoted regiospecific 1,6-hydroarylation of para-quinone methides with N-heteroarenes: Synthesis of unsymmetrical triarylmethanes

Tetrahedron, Год журнала: 2024, Номер 158, С. 133982 - 133982

Опубликована: Апрель 7, 2024

Язык: Английский

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Catalyst‐ and Additive‐free, Regioselective 1,6‐Hydroarylation of para‐Quinone Methides with Anilines in HFIP

Chemistry - An Asian Journal, Год журнала: 2023, Номер 18(23)

Опубликована: Окт. 17, 2023

A simple and efficient method for the synthesis of diarylmethyl-functionalized anilines through hexafluoroisopropanol (HFIP)-mediated regioselective 1,6-hydroarylation reaction para-quinone methides (p-QMs) with under catalyst- additive-free conditions is reported. Various kinds p-QMs amines (e. g. primary, secondary tertiary amines) are well tolerated in this transformation without pre-protection amino group, corresponding products could be generated good to excellent yields satisfactory regioselectivity optimized conditions. In addition adaptable amine compounds, indoles their derivatives also compatible system. This can easily extended a gram scale-synthesis level synthesize target product. Furthermore, it worth noting that some complex small aniline molecules biological activity selectively modified using method. The possible mechanism proposed step-by-step control experiments DFT calculations, showing key process achieving hydrogen bonding effect HFIP substrates.

Язык: Английский

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Acetic Acid‐Catalyzed 1,6‐Addition of Indolizine to para‐Quinone Methides

Asian Journal of Organic Chemistry, Год журнала: 2023, Номер 12(7)

Опубликована: Май 31, 2023

Abstract This article describes the development of a metal and additive‐free protocol that utilizes acetic acid (AcOH) as catalyst for C3‐alkylation indolizines using para ‐Quinone Methides ( p ‐QMs) an alkylation agent. The additive free method offers easy route to various substituted indolizine derivatives with good functional group tolerance delivering acceptable yields (up 93%). A gram‐scale synthesis further product derivatization show synthetic potential this technique. significance these findings medicinal chemistry makes green approach relevant both organic chemists, given crucial role in pharmaceutical industry.

Язык: Английский

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HBF₄‐Catalyzed 3,6‐Bis‐diarylmethylation of Carbazoles withpara‐Quinone Methides

European Journal of Organic Chemistry, Год журнала: 2022, Номер 2022(46)

Опубликована: Ноя. 15, 2022

Abstract In this article, we demonstrate an atom economical, practical, mild and selective HBF 4 ‐catalyzed 1,6‐conjugate addition of carbazoles to para ‐Quinone Methides ( p ‐QMs) access 3,6‐bis‐diarylmethyl‐ mono‐diarylmethyl carbazoles. This metal additive free protocol provides convenient the substituted carbazole derivatives in moderate excellent yields with a good functional group tolerance. It was found that couple 3,6‐disubstituted showed interesting photophysical properties and, therefore, might potentially find some applications as host materials OLEDs.

Язык: Английский

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Photoinduced decarboxylative 1,6-addition of para-quinone methides with α-keto acids: an eco-friendly approach to α,α′-diarylated ketones

New Journal of Chemistry, Год журнала: 2022, Номер 46(44), С. 21032 - 21036

Опубликована: Янв. 1, 2022

The photoinduced decarboxylative 1,6-addition of para -quinone methides with α-keto acids in an eco-friendly approach to α,α′-diarylated ketones is developed.

Язык: Английский

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Acid‐Catalyzed Regioselective Synthesis of α‐Diarylmethyl Substituted Phenols and para‐Quinone Methides in Water

Asian Journal of Organic Chemistry, Год журнала: 2022, Номер 11(8)

Опубликована: Июль 2, 2022

Abstract A facile and efficient method for the synthesis of α ‐diarylmethyl substituted phenols from para ‐quinone methides ( p ‐QMs) with has been developed by using phosphoric acid as catalyst water green solvent under mild conditions. In addition, when TEMPO was added an additive reaction, diaryl‐substituted could be generated target product. The reactions show high functional group tolerance, good to excellent yields unique selectivity, a broad range motif containing phenol(s) quinones prepared through divergent methods. Furthermore, series control experiments were performed gain insights plausible mechanisms. These protocols have atomic economy, may significant implications construction C( sp 3 )−C( 2 ) bonds in organic synthesis.

Язык: Английский

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Ruthenium-Catalyzed 1,6-Hydroalkylation of para-Quinone Methides with Ketones via the in Situ Activation of C(sp³)–H Bonds

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(23), С. 16196 - 16215

Опубликована: Ноя. 13, 2023

A simple and efficient method for the ruthenium-catalyzed 1,6-hydroalkylation of para-quinone methides (p-QMs) with ketones via in situ activation C(sp3)-H bonds has been disclosed. Without need preactivation substrates oxidant, a broad range p-QMs are well tolerated, producing expected products moderate to good yields. Step-by-step control experiments DFT calculation were conducted systematically gain insights plausible reaction mechanism. This finding may have potential application selective diarylmethylation at α-C position organic synthesis.

Язык: Английский

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Six-membered ring systems: pyridines and benzo derivatives

Progress in heterocyclic chemistry, Год журнала: 2023, Номер unknown, С. 383 - 425

Опубликована: Янв. 1, 2023

Язык: Английский

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