Kinetic Resolution of Racemic Radicals in Asymmetric Photoredox Minisci Reactions with Azaarenes for Precise Construction of Two Non-adjacent Stereocenters DOI
Tianju Shao,

Feiyun Nie,

Shanshan Cao

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

Despite the significant potential of photocatalysis as a robust synthetic tool, high reactivity radicals often presents challenges in achieving optimal chemoselectivity. In this study, we demonstrate that inherent limitation can be strategically harnessed for asymmetric photoredox catalysis. By utilizing chiral catalyst to facilitate kinetic resolution between two enantiomers racemic radical intermediates, one enantiomer selectively undergoes desired transformation, while noncatalytic side reactions deplete other enantiomer. Consequently, an attractive three-component Minisci-type reaction involving bromides, homoallylic tertiary alcohols or amines, and azaarenes has been developed. This approach enables efficient assembly amines onto nonadjacent β-position azaarene-functionalized carbon stereogenic center with levels enantio- diastereoselectivity. Therefore, method not only allows direct utilization readily available feedstocks are challenging convert into prochiral via redox processes but also provides strategy synthesizing complex molecules multiple stereocenters.

Language: Английский

Kinetic Resolution of Racemic Radicals in Asymmetric Photoredox Minisci Reactions with Azaarenes for Precise Construction of Two Non-adjacent Stereocenters DOI
Tianju Shao,

Feiyun Nie,

Shanshan Cao

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

Despite the significant potential of photocatalysis as a robust synthetic tool, high reactivity radicals often presents challenges in achieving optimal chemoselectivity. In this study, we demonstrate that inherent limitation can be strategically harnessed for asymmetric photoredox catalysis. By utilizing chiral catalyst to facilitate kinetic resolution between two enantiomers racemic radical intermediates, one enantiomer selectively undergoes desired transformation, while noncatalytic side reactions deplete other enantiomer. Consequently, an attractive three-component Minisci-type reaction involving bromides, homoallylic tertiary alcohols or amines, and azaarenes has been developed. This approach enables efficient assembly amines onto nonadjacent β-position azaarene-functionalized carbon stereogenic center with levels enantio- diastereoselectivity. Therefore, method not only allows direct utilization readily available feedstocks are challenging convert into prochiral via redox processes but also provides strategy synthesizing complex molecules multiple stereocenters.

Language: Английский

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