N-Heterocyclic nitrenium-catalyzed photoreductive radical-polar crossover for alkene dicarbofunctionalization

Han, Youfeng; Zhang, Beibei; Wang, Zhixiang; Chen, Xiangyu

doi:10.1016/j.gresc.2024.03.002

Green Synthesis and Catalysis

2024

DOI: 10.1016/j.gresc.2024.03.002

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N-Heterocyclic nitrenium-catalyzed photoreductive radical-polar crossover for alkene dicarbofunctionalization

Youfeng Han,

Beibei Zhang,

Zhixiang Wang

et al.

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2024

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Cited by 3 publications

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Radical Replacement Process for Ligated Boryl Radical-Mediated Activation of Unactivated Alkyl Chlorides for C(sp³)–C(sp³) Bond Formation

Fang,

Zhang,

et al. 2024

J. Am. Chem. Soc.

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The ligated boryl radical (LBR) has emerged as a potent tool for activating alkyl halides in radical transformations through halogen-atom transfer (XAT). However, unactivated alkyl chlorides still present an open challenge for this strategy. We herein describe a new activation mode of the LBR for the activation of unactivated alkyl chlorides to construct a C(sp3)–C(sp3) bond. Mechanistic studies reveal that the success of the protocol relies on a radical replacement process between the LBR and unactivated alkyl chloride, forming an alkyl borane intermediate as the alkyl radical precursor. Aided with the additive K3PO4, the alkyl borane then undergoes one-electron oxidation, generating an alkyl radical. The incorporation of the radical replacement activation model to activate unactivated alkyl chlorides significantly enriches LBR chemistry, which has been applied to activate alkyl iodides, alkyl bromides, and activated alkyl chlorides via XAT.

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Radical Replacement Process for Ligated Boryl Radical-Mediated Activation of Unactivated Alkyl Chlorides for C(sp³)–C(sp³) Bond Formation

Fang,

Zhang,

et al. 2024

J. Am. Chem. Soc.

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Alkene Carboxy-Alkylation via CO₂^•–

Dang,

Han,

Chmiel

et al. 2024

J. Am. Chem. Soc.

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Herein, we introduce a new platform for alkene carboxy-alkylation. This reaction is designed around CO 2 •− addition to alkenes followed by radical polar crossover, which enables alkylation through carbanion attack on carbonyl electrophiles. We discovered that CO 2•− adds to alkenes faster than it reduces carbonyl electrophiles and that this reactivity can be exploited by accessing CO 2•− via hydrogen atom transfer from formate. This photocatalytic system transforms vinylarenes and carbonyl compounds into a diverse array of substituted γ-lactone products. Furthermore, indoles can be engaged through dearomative carboxy-alkylation, delivering medicinally relevant C(sp 3 )-rich heterocyclic scaffolds. Mechanistic studies reveal that the active photocatalyst is generated in situ through a photochemically induced reaction between the precatalyst and DMSO. Overall, we have developed a three-component alkene carboxy-alkylation reaction enabled by the use of formate as the CO 2•− precursor.

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Recent Advances in Combining Photo- and N-Heterocycle Nitrenium Catalysis

Tu,

Chen,

2024

Synthesis

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N-Heterocyclic nitreniums (NHNs) are isoelectronic and isostructural analogues of N-heterocyclic carbenes (NHCs). Unlike NHCs, NHNs are much less developed. While a comprehensive understanding of NHN reactivity remains elusive, recent advancements have demonstrated their utility as Lewis acid catalysts, photoreductants, and photooxidants, leading to several reaction patterns. In this short review, we focus on the applications of NHNs in photoredox reactions. We also discuss the mechanisms behind these transformations and outline future research directions.1 Introduction2 Application of N-Heterocyclic Nitreniums as Photoreductants3 Application of N-Heterocyclic Nitreniums to Facilitate Photohomolysis4 Application of N-Heterocyclic Nitreniums as Photooxidants5 Conclusion

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N-Heterocyclic nitrenium-catalyzed photoreductive radical-polar crossover for alkene dicarbofunctionalization

Cited by 3 publications

References 77 publications

Radical Replacement Process for Ligated Boryl Radical-Mediated Activation of Unactivated Alkyl Chlorides for C(sp³)–C(sp³) Bond Formation

Radical Replacement Process for Ligated Boryl Radical-Mediated Activation of Unactivated Alkyl Chlorides for C(sp³)–C(sp³) Bond Formation

Alkene Carboxy-Alkylation via CO₂^•–

Recent Advances in Combining Photo- and N-Heterocycle Nitrenium Catalysis

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N-Heterocyclic nitrenium-catalyzed photoreductive radical-polar crossover for alkene dicarbofunctionalization

Cited by 3 publications

References 77 publications

Radical Replacement Process for Ligated Boryl Radical-Mediated Activation of Unactivated Alkyl Chlorides for C(sp3)–C(sp3) Bond Formation

Radical Replacement Process for Ligated Boryl Radical-Mediated Activation of Unactivated Alkyl Chlorides for C(sp3)–C(sp3) Bond Formation

Alkene Carboxy-Alkylation via CO2•–

Recent Advances in Combining Photo- and N-Heterocycle Nitrenium Catalysis

Contact Info

Product

Resources

About

Radical Replacement Process for Ligated Boryl Radical-Mediated Activation of Unactivated Alkyl Chlorides for C(sp³)–C(sp³) Bond Formation

Radical Replacement Process for Ligated Boryl Radical-Mediated Activation of Unactivated Alkyl Chlorides for C(sp³)–C(sp³) Bond Formation

Alkene Carboxy-Alkylation via CO₂^•–