Ni-catalyzed benzylic β-C(sp3)–H bond activation of formamides

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Дек. 22, 2022

The development of transition metal-catalyzed β-C-H bond activation via highly-strained 4-membered metallacycles has been a formidable task. So far, only scarce examples have reported to undergo metallacycles, and all them rely on precious metals. In contrast, earth-abundant inexpensive 3d still remains an elusive challenge. Herein, we report phosphine oxide-ligated Ni-Al bimetallic catalyst activate secondary benzylic C(sp3)-H bonds formamides nickelacycles, providing series α,β-unsaturated γ-lactams in up 97% yield.

Язык: Английский

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Access to distal meta-C–H functionalization of arylmethanesulfonic acid derivatives

Chemical Communications, Год журнала: 2023, Номер 59(59), С. 9106 - 9109

Опубликована: Янв. 1, 2023

Herein, we report the meta-C-H olefination of arylmethanesulfonates aided by a potentially versatile aliphatic nitrile-directing group under microwave irradiation conditions with fair to very good yields and outstanding regioselectivities. Significantly, protocol showed broad substrate scope including olefin-derived drugs cyclic olefins. Remarkably, dual bond was amenable generating bis-olefination products.

Язык: Английский

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Palladium catalyzed remote-meta-C–H functionalization of aniline scaffolds

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(5), С. 1473 - 1478

Опубликована: Янв. 1, 2024

Here, we report on a microwave-assisted accelerated meta -C–H olefination of aniline derivatives using simple aliphatic end-on nitrile assembly. Notably, the protocol shows broad substrate compatibility with remarkable regio-selectivity.

Язык: Английский

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Palladium (II)‐Catalyzed C−H Activation with Bifunctional Ligands: From Curiosity to Industrialization

Angewandte Chemie, Год журнала: 2024, Номер 136(19)

Опубликована: Фев. 29, 2024

Abstract In 2001, our curiosity to understand the stereochemistry of C−H metalation with Pd prompted first studies in Pd(II)‐catalyzed asymmetric activation (RSC Research appointment: 020 7451 2545, Grant: RG 36873, Dec. 2002). We identified four central challenges: 1. poor reactivity simple salts native substrates; 2. few strategies control site selectivity for remote bonds; 3. lack chiral catalysts achieve enantioselectivity via metalation, and 4. low practicality due limited coupling partner scope use specialized oxidants. These challenges necessitated new catalyst reaction development. For , we developed approaches enhance substrate–catalyst affinity together novel bifunctional ligands which participate accelerate cleavage step. site‐selectivity introduced concept systematically modulating distance geometry between a directing template, catalyst, substrate selectively access bonds. devised predictable stereomodels catalyst‐controlled enantioselective based on participation ligands. Finally, have varied catalytic manifolds Pd(II) accommodate diverse partners while employing practical oxidants such as peroxides. advances culminated numerous reactions, setting stage broad industrial applications.

Язык: Английский

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Dirhodium-catalyzed one-step cascade intermolecular 1,4-diamination via cyclopropanation

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(17), С. 4769 - 4778

Опубликована: Янв. 1, 2024

A step-economical 1,4-diamine synthesis from aromatic hydrocarbons via arylcyclopropane intermediates is reported. Using a Rh 2 /NFSI system, multiple C(sp 3 )–H bonds are activated in single-step cascade, showing the catalyst's versatility.

Язык: Английский

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