Enantioselective Synthesis of Axially Chiral Allylic Nitriles via Nickel‐Catalyzed Desymmetric Cyanation of Biaryl Diallylic Alcohols

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 18, 2024

Axially chiral nitriles are common motifs in organic photoelectric materials, biological compounds, and agrochemicals. Unfortunately, the limited synthetic approaches to axially have impeded their availability. Herein, we report first nickel-catalyzed desymmetric allylic cyanation of biaryl alcohols for synthesis nitrile structures high yields with excellent enantioselectivities (up 90 % yield >99 ee). This process enables a diverse range bearing β,γ-unsaturated alcohol moieties. Leveraging cyano groups as versatile functionalization handles allow further derivatization these frameworks. Density functional theory (DFT) calculations suggest that both steric electronic interactions play crucial roles determining enantioselectivity this transformation. Moreover, mild facile protocol is also applicable gram-scale preparation nitriles.

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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Nickel‐Catalyzed Atroposelective Carbo‐Carboxylation of Alkynes with CO2: En Route to Axially Chiral Carboxylic Acids

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 137(1)

Published: Nov. 7, 2024

Abstract Precise synthesis of carboxylic acids via catalytic carboxylation with CO 2 is highly appealing. Although considerable advancements have been achieved in difunctionalizing unsaturated hydrocarbons, the asymmetric variants are conspicuously underdeveloped, particularly addressing axially chiral alkenes. Herein, we report first atroposelective alkynes . A variety valuable obtained good yields and high chemo‐, regio‐, Z/E enantio‐selectivities. Notably, an unexpected anti ‐selective carbo‐carboxylation observed sp ‐hybrid carbo‐electrophile‐initiated reductive alkynes. Mechanistic studies including DFT calculation elucidate origin induction ‐selectivity vinyl‐carboxylation

Language: Английский

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Highly efficient and cis-selective carbofunctionalization of internal alkynes catalyzed by palladium a-diimine complexes

Molecular Catalysis, Journal Year: 2023, Volume and Issue: 549, P. 113493 - 113493

Published: Aug. 26, 2023

Language: Английский

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Atroposelective Three-Component (Fluoro)methylative Alkylation of Terminal Alkynes

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 63 - 71

Published: Dec. 13, 2024

The development of synthetic methods for the selective installation methyl and fluoromethyl groups is highly desired due to their critical role in drug development. While significant advances have been made methylation difluoromethylation aromatic compounds, catalytic atroposelective (fluoro)methylative functionalization alkynes forge axially chiral alkenes remains underexploited. Herein, we report an enantioselective cross-electrophile strategy efficient 1,2-carbo-(fluoro)methylation with two different alkyl halides via nickel catalysis. By integrating a one-electron radical process two-electron organometallic process, this protocol employs simple catalyst effectively discriminate between secondary tertiary (fluoro)methyl alkyne difunctionalization. This demonstrates good compatibility activated secondary/tertiary bromides, terminal alkynes, halides, permitting straightforward synthesis broad range synthetically valuable (fluoro)methyl-substituted high chemo-, regio-, trans-, atropo-selectivity. Preliminary mechanistic studies provide insight into potential reaction pathway.

Language: Английский

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Synthesis of Axially Chiral Vinyl Halides via Cu(I)-Catalyzed Enantioselective Radical 1,2-Halofunctionalization of Terminal Alkynes

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 502 - 513

Published: Dec. 20, 2024

Organohalides are crucial in modern organic synthesis, thanks to their robust and versatile reactivity cross-coupling other key transformations. However, catalytic asymmetric methods for producing enantioenriched organohalides, particularly axially chiral vinyl halides, remain underdeveloped. Here, we present a Cu(I)-catalyzed, highly enantioselective radical alkyne 1,2-halofunctionalization, utilizing custom-designed tridentate anionic N,N,N-ligands with bulky peripheral substituents. This method efficiently employs (hetero)aryl alkyl sulfonyl chlorides, as well α-carbonyl bromides, precursors utilizes diverse range of 2-amino 2-oxy aryl terminal alkynes substrates produce halides. The reaction is scalable gram quantities, the halides can be further transformed into thiourea, pyridyl carboxamide, quinolyl sulfonamide compounds, some which show significant potential catalysis. Both experimental theoretical mechanistic studies support an halogen atom transfer mechanism. opens avenue accessing facilitating broad applications various related fields.

Language: Английский

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Reductive Dicarbofunctionalization of C–C π-Bonds

Elsevier eBooks, Journal Year: 2023, Volume and Issue: unknown

Published: Jan. 1, 2023

Language: Английский

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