Intermolecular Asymmetric Arylative Dearomatization of 1-Naphthols DOI Creative Commons

Max Kadarauch,

Tom Moss, Robert J. Phipps

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Дек. 4, 2024

Arylative dearomatization forms quaternary stereocenters in cyclic systems with the concomitant introduction of an aromatic ring. Pd-catalyzed arylative dearomatization, which uses conditions analogous to cross-coupling, has emerged as a powerful method intramolecular context. But translating this from cyclizations intermolecular process proven extremely challenging: examples are scarce, and those that exist have not been rendered enantioselective, despite potential for broad application medicinal chemistry natural product synthesis. We describe strategy utilizes attractive interactions between ligand substrate overcome challenge promote intermolecular, highly enantioselective naphthols using range aryl bromide electrophiles. Crucial success is use readily accessed sulfonated chiral phosphine sSPhos, we believe engages electrostatic substrate. Not only does sSPhos control enantioselectivity but it also drastically accelerates reaction, most likely by facilitating challenging palladation step initiates dearomatization.

Язык: Английский

Intermolecular Asymmetric Arylative Dearomatization of 1-Naphthols DOI Creative Commons

Max Kadarauch,

Tom Moss, Robert J. Phipps

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Дек. 4, 2024

Arylative dearomatization forms quaternary stereocenters in cyclic systems with the concomitant introduction of an aromatic ring. Pd-catalyzed arylative dearomatization, which uses conditions analogous to cross-coupling, has emerged as a powerful method intramolecular context. But translating this from cyclizations intermolecular process proven extremely challenging: examples are scarce, and those that exist have not been rendered enantioselective, despite potential for broad application medicinal chemistry natural product synthesis. We describe strategy utilizes attractive interactions between ligand substrate overcome challenge promote intermolecular, highly enantioselective naphthols using range aryl bromide electrophiles. Crucial success is use readily accessed sulfonated chiral phosphine sSPhos, we believe engages electrostatic substrate. Not only does sSPhos control enantioselectivity but it also drastically accelerates reaction, most likely by facilitating challenging palladation step initiates dearomatization.

Язык: Английский

Процитировано

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