Cobalt-Catalyzed Hydrocyanation of Methylenecyclopropanes to Homoallylic Nitriles

Jiao, Mingdong; Fang, Xianjie

doi:10.1021/acs.orglett.2c03726

Org. Lett.

2022

DOI: 10.1021/acs.orglett.2c03726

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Cobalt-Catalyzed Hydrocyanation of Methylenecyclopropanes to Homoallylic Nitriles

Mingdong Jiao

Xianjie Fang

Abstract: We describe herein a novel synthesis of various homoallylic nitriles via cobalt-catalyzed hydrocyanation of methylenecyclopropanes. Excellent selectivity, mild reaction conditions, good functional group compatibility, gram-scale reaction, and product transformations demonstrate the power of this protocol. This extraordinary selectivity can probably be attributed to the stronger aptitude of the alkyl−cobalt cyanide intermediate to undergo reductive elimination rather than βhydride elimination.

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Cited by 8 publications

References 35 publications

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Enantio‐ and Regioselective Cascade Hydroboration of Methylenecyclopropanes for Facile Access to Chiral 1,3‐ and 1,4‐Bis(boronates)

Zhou,

Meng,

Yang

et al. 2024

Advanced Science

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Chiral 1, n‐bis(boronate) plays a crucial role in organic synthesis and medicinal chemistry. However, their catalytic and asymmetric synthesis has long posed a challenge in terms of operability and accessibility from readily available substrates. The recent discovery of the C═C bond formation through β‐C elimination of methylenecyclopropanes (MCP) has provided an exciting opportunity to enhance molecular complexity. In this study, the catalyzed asymmetric cascade hydroboration of MCP is developed. By employing different ligands, various homoallylic boronate intermediate are obtained through the hydroboration ring opening process. Subsequently, the cascade hydroboration with HBpin or B2pin2 resulted in the synthesis of enantioenriched chiral 1,3‐ and 1,4‐bis(boronates) in high yields, accompanied by excellent chemo‐ and enantioselectivities. The selective transformation of these two distinct C─B bonds also demonstrated their application potential in organic synthesis.

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Enantio‐ and Regioselective Cascade Hydroboration of Methylenecyclopropanes for Facile Access to Chiral 1,3‐ and 1,4‐Bis(boronates)

Zhou,

Meng,

Yang

et al. 2024

Advanced Science

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Palladium‐Catalyzed Enantio‐ and Regioselective Ring‐Opening Hydrophosphinylation of Methylenecyclopropanes

et al. 2023

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Transition metal‐catalyzed hydrofunctionalization of methylenecyclopropanes (MCPs) has presented a considerable challenge due to the difficult manipulation of regioselectivity and complicated reaction patterns. Herein, we report a straightforward Pd‐catalyzed ring‐opening hydrophosphinylation reaction of MCPs via highly selective C−C bond cleavage. This method allows for rapid and efficient access to a wide range of chiral allylic phosphine oxides in good yields and high enantioselectivities. Additionally, density functional theory (DFT) calculations were performed to elucidate the reaction mechanism and the origin of enantioselectivity.

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Nickel‐Catalyzed Regio‐ and Enantioselective Migratory Hydrocyanation of Internal Alkenes: Expanding the Scope to α,ω‐Diaryl Internal Alkenes

Jiao,

Long,

Chen

et al. 2024

Angewandte Chemie

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Metal‐hydride‐catalyzed migratory functionalization of alkenes witnessed extensive development in the past few years. However, the asymmetric version of this reaction has remained largely underdeveloped owing to the difficulty in simultaneous control of both regio‐ and stereoselectivity. In addition, exploring the wider alkene substrate scope to enable more synthetically valuable applications represents another challenge in this field. In this context, a nickel‐catalyzed asymmetric hydrocyanation of internal alkenes involving a chain‐walking process is demonstrated. The reaction exhibits excellent regio‐ and enantioselectivity, proceeds under mild reaction conditions, and delivers benzylic nitriles in high yields. Even α,ω‐diaryl internal alkenes, which are known to be one of the most challenging substrates of this type, could be successfully converted to the desired products with good regio‐ and stereoselectivity by modifying the electronic and steric effects. Theoretical calculations suggest that the η3‐benzyl coordination mode and the aryl substituent (3,5‐(OMe)2C6H3) on the diphosphite ligand are both key factors in regulating regio‐ and enantioselectivity.

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Cobalt-Catalyzed Hydrocyanation of Methylenecyclopropanes to Homoallylic Nitriles

Cited by 8 publications

References 35 publications

Enantio‐ and Regioselective Cascade Hydroboration of Methylenecyclopropanes for Facile Access to Chiral 1,3‐ and 1,4‐Bis(boronates)

Enantio‐ and Regioselective Cascade Hydroboration of Methylenecyclopropanes for Facile Access to Chiral 1,3‐ and 1,4‐Bis(boronates)

Palladium‐Catalyzed Enantio‐ and Regioselective Ring‐Opening Hydrophosphinylation of Methylenecyclopropanes

Nickel‐Catalyzed Regio‐ and Enantioselective Migratory Hydrocyanation of Internal Alkenes: Expanding the Scope to α,ω‐Diaryl Internal Alkenes

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