Merging SOMO activation with transition metal catalysis: Deoxygenative functionalization of amides to β-aryl amines

Science Advances, Journal Year: 2025, Volume and Issue: 11(3)

Published: Jan. 17, 2025

Singly occupied molecular orbital (SOMO) activation of in situ generated enamines has achieved great success (asymmetric) α-functionalization carbonyl compounds. However, examples on the use this mode transformations other functional groups are rare, and combination SOMO with transition metal catalysis is still less explored. In area deoxygenative functionalization amides, intermediates such as iminium ions were often to result formation α-functionalized amines. contrast, direct deoxygenation amides β-functionalized amines highly appealing yet remains scarcely investigated. Here, a arylation aryl halides was developed via multicatalysis iridium/photoredox/nickel/iridium, affording β-aryl high efficiency. The key reaction enamine synergy Ni-catalyzed arylation, which conjunction two compatible Ir-catalyzed reduction processes.

Language: Английский

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Modular Access to Chiral Benzylamines via Ni/Photoredox-Catalyzed Multicomponent Cross-Electrophile Coupling

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 30, 2025

A Ni/photoredox dual-catalyzed multicomponent cross-electrophile coupling of N-vinyl amides with (hetero)aryl halides and (2°, 3°)-alkyl redox-active esters in the presence cheap reductant Hantzsch ester is reported here. This reductive protocol provides direct access to various synthetically challenging chiral α-arylamides good yields excellent enantioselectivities (up 99% ee, majority exceeding 97% ee), which can be further derived into primary secondary amines. Preliminary experimental studies shed light on potential catalytic pathways.

Language: Английский

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Synthesis of α-Chloroboronic Esters via Photoredox-Catalyzed Chloro-Alkoxycarbonylation of Vinyl Boronic Esters

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 9, 2025

α-Chloroboronic esters are a class of stable multifunctional molecules that show unique applications in pharmaceutical science and organic chemistry. Despite their apparent utility, the synthetic methods these compounds remain limited. Herein, novel strategy for efficient synthesis α-chloroboronic is developed via photoredox-catalyzed chloro-alkoxycarbonylation vinyl boronic esters. This features advantages high atom economy, environmental friendliness, excellent functional group compatibility was verified by cross-coupling variety free alcohols, oxalyl chlorides, Control experiments mechanistic studies indicate alkoxycarbonyl radical α-boryl carbocation key intermediates this transformation.

Language: Английский

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Nickel-Catalyzed Enantioselective Three-Component 1,2-Alkylarylation of Alkenes with Arylboronic Acids as Arylation Reagents

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7833 - 7841

Published: April 25, 2025

Language: Английский

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