Transition-Metal and Photocatalyst-Free, Redox-Neutral Heteroarylation of C(sp³)–H Bonds

ACS Catalysis, Год журнала: 2024, Номер 14(16), С. 12664 - 12670

Опубликована: Авг. 7, 2024

Developing a transition-metal-free system for functionalizing the C(sp3)–H bond has posed long-standing challenge in synthetic organic chemistry and is of significance drug discovery. In this context, we present straightforward protocol heteroarylation benzylic alpha-amino C–H bonds, achieved without transition metals or photocatalysts. A pivotal aspect redox-neutral hydroarylation utilization commercially available triisopropylsilanethiol (iPr3SiSH) as an organocatalyst. This organocatalyst serves dual function forming electron donor–acceptor complex (EDA) acting hydrogen atom transfer catalyst, generating alkyl/benzylic radicals from corresponding bonds. Applying mild methodology, various amino bonds were functionalized to give C(sp2)–heteroaryl C–C cross-coupled product. To demonstrate practical utility protocol, pyridine was incorporated into molecule via late-stage modification. Additionally, gram-scale reaction also performed show advantages protocol.

Язык: Английский

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Cu-Catalyzed Regioselective C–H Amination of 2H-Indazoles for the Synthesis of Indazole-Containing Indazol-3(2H)-ones

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(9), С. 5731 - 5744

Опубликована: Март 30, 2023

A copper-catalyzed C3 amination of 2H-indazoles with and indazol-3(2H)-ones under mild conditions was developed. series indazole-containing indazol-3(2H)-one derivatives were produced in moderate to excellent yields. The mechanistic studies suggest that the reactions probably proceed through a radical pathway.

Язык: Английский

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Selective Oxidative Methyl C–H Functionalization of Butylated Hydroxytoluene toward Arylimines/N-Heterocycles

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(20), С. 14649 - 14658

Опубликована: Окт. 10, 2023

A metal-free and selective oxidative methyl C-H functionalization of BHT with aniline compounds has been developed. This innovative method enables the facile efficient synthesis a diverse array BHT-functionalized N-containing skeletons, including arylamines, benzoxazoles, benzothiazoles, benzimidazoles, quinazolines, quinazolinones, all which are challenging to access. The control experiment involving TEMP18O suggests that radical adduct TEMPO benzyl may serve as an intermediate.

Язык: Английский

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Five-membered ring systems: with more than one N atom

Progress in heterocyclic chemistry, Год журнала: 2023, Номер unknown, С. 281 - 332

Опубликована: Янв. 1, 2023

Язык: Английский

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