Copper-Catalyzed Enantioconvergent Radical N-Alkylation of Diverse (Hetero)aromatic Amines DOI
Xuan‐Yi Du,

Jia‐Heng Fang,

Ji‐Jun Chen

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 9444 - 9454

Опубликована: Март 21, 2024

The 3d transition metal-catalyzed enantioconvergent radical cross-coupling provides a powerful tool for chiral molecule synthesis. In the classic mechanism, bond formation relies on interaction between nucleophile-sequestered metal complexes and radicals, limiting nucleophile scope to sterically uncongested ones. coupling of congested nucleophiles poses significant challenge due difficulties in transmetalation, restricting reaction generality. Here, we describe probable outer-sphere nucleophilic attack mechanism that circumvents challenging transmetalation associated with nucleophiles. This strategy enables general copper-catalyzed N-alkylation aromatic amines secondary/tertiary alkyl halides exhibits catalyst-controlled stereoselectivity. It accommodates diverse amines, especially bulky secondary primary ones deliver value-added (>110 examples). is expected inspire more nucleophiles, particularly ones, accelerate

Язык: Английский

Copper-Catalyzed Enantioconvergent Radical N-Alkylation of Diverse (Hetero)aromatic Amines DOI
Xuan‐Yi Du,

Jia‐Heng Fang,

Ji‐Jun Chen

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 9444 - 9454

Опубликована: Март 21, 2024

The 3d transition metal-catalyzed enantioconvergent radical cross-coupling provides a powerful tool for chiral molecule synthesis. In the classic mechanism, bond formation relies on interaction between nucleophile-sequestered metal complexes and radicals, limiting nucleophile scope to sterically uncongested ones. coupling of congested nucleophiles poses significant challenge due difficulties in transmetalation, restricting reaction generality. Here, we describe probable outer-sphere nucleophilic attack mechanism that circumvents challenging transmetalation associated with nucleophiles. This strategy enables general copper-catalyzed N-alkylation aromatic amines secondary/tertiary alkyl halides exhibits catalyst-controlled stereoselectivity. It accommodates diverse amines, especially bulky secondary primary ones deliver value-added (>110 examples). is expected inspire more nucleophiles, particularly ones, accelerate

Язык: Английский

Процитировано

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