Chromium‐ and Metal‐Reductant‐Free Asymmetric Nozaki–Hiyama–Kishi (NHK) Reaction Enabled by Metallaphotoredox Catalysis

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(37)

Published: June 25, 2024

Abstract Chiral allylic alcohols are highly prized in synthetic chemistry due to their versatile reactivity stemming from both alkenyl and hydroxyl functionalities. While the Nozaki–Hiyama–Kishi (NHK) reaction is a widely used method for synthesis of alcohols, it suffers drawbacks such as use toxic chromium salts, high amounts metal reductants, poor enantiocontrol. To address these limitations, we present novel approach involving metallaphotoredox‐catalyzed asymmetric NHK production chiral alcohols. This marries (pseudo)halides with aldehydes, leveraging synergistic blend nickel catalyst photocatalyst. innovative technique enables oxidative addition insertion just using nickel, diverging significantly conventional pathway mediated by salts. The adoption this methodology holds immense promise crafting spectrum intricate compounds, particularly those significance pharmaceuticals. Detailed experimental investigations have shed light on metallaphotoredox process, further enhancing our understanding enabling advancements.

Language: Английский

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Nickel-Catalyzed Atroposelective Reductive [2 + 4] Annulation toward Synthesis of Axially Chiral Biaryls

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(22), P. 17039 - 17045

Published: Nov. 4, 2024

Herein, we demonstrate the successful application of reductive [2 + 4] annulation in atroposelective de novo benzene ring formation. This nickel-catalyzed reaction between β-substituted α-naphthylalkynes and a biselectrophile C(sp2)–X type offers an efficient convenient method to prepare highly enantioenriched C1-symmetric axially chiral biaryls containing two preinstalled functionalities. The coupling products can be used as versatile synthetic intermediates access bidentate ligands or bifunctional organocatalysts, their utility asymmetric catalysis is also showcased this context.

Language: Английский

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Cobalt-Catalyzed Reductive Arylation of N-Sulfonyl Imines

Synfacts, Journal Year: 2023, Volume and Issue: 19(07), P. 0679 - 0679

Published: June 16, 2023

Key words cobalt catalysis - N-sulfonyl imines arylation

Language: Английский

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