Nickel-Catalyzed Cyanation of Allylic Alcohols: High Degree of Chiral Inversion in Aqueous Reaction Media

Liu, Yaxin; Hu, Jiawen; Long, Jinguo; Liu, Xuefen; Luo, Shu-Ping; Fang, Xianjie

doi:10.1021/acs.orglett.4c02211

Org. Lett.

2024

DOI: 10.1021/acs.orglett.4c02211

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Nickel-Catalyzed Cyanation of Allylic Alcohols: High Degree of Chiral Inversion in Aqueous Reaction Media

Yaxin Liu,

Jiawen Hu,

Jinguo Long

et al.

Abstract: Nickel-catalyzed aqueous cyanation of allylic alcohols is herein described. This catalytic protocol provided environmentally friendly and operationally simple access to a variety of allylic nitriles in good yields. For chiral allylic alcohols, the reaction gave chiral allylic nitriles with a high degree of chiral inversion. The accelerated release of cyanide in H2O was crucial for the success of this reaction.

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2024

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Cited by 3 publications

References 34 publications

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

Li,

Song,

Wang

et al. 2024

Angewandte Chemie

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

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

Li,

Song,

Wang

et al. 2024

Angewandte Chemie

View full text Add to dashboard Cite

show abstract

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

Li,

Song,

Wang

et al. 2024

Angew Chem Int Ed

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Heteroarylation of Organophosphonium Salts with Indoles in Water: Synthesis of Symmetrical and Unsymmetrical 3,3′‐Bisindolylmethane Derivatives.

Luo,

Ji,

et al. 2024

Eur J Org Chem

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A method for the synthesis of symmetrical and unsymmetrical 3,3'‐bis(indolyl)methanes (3,3'‐BIMs) has been developed through the direct heteroarylation of indolyl‐containing di(hetero)aryl phosphonium salts with indole derivatives in aqueous media. This metal‐free reaction proceeds smoothly under mild conditions, eliminating the need for hazardous solvents and expensive additives/catalysts typically used in conventional synthesis routes, thereby highlighting the synthetic practicality and efficiency of the process. The success of this approach is largely attributed to the role of water as a promoter, facilitating the C‐P bond functionalization of the phosphonium salts. Furthermore, the reaction demonstrates a broad substrate scope, good functional group tolerance, and excellent scalability. Moreover, the protocol can also be extended to the synthesis of triindolylmethane compound and diarylmethylated indole.

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Nickel-Catalyzed Cyanation of Allylic Alcohols: High Degree of Chiral Inversion in Aqueous Reaction Media

Cited by 3 publications

References 34 publications

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

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

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

Heteroarylation of Organophosphonium Salts with Indoles in Water: Synthesis of Symmetrical and Unsymmetrical 3,3′‐Bisindolylmethane Derivatives.

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