Sacrificial Anode-Free Electrochemical Cross-Electrophile Coupling of 1,3-Diol Derivatives to Form Aliphatic and Aryl Cyclopropanes

Hirbawi, Nadia; Raffman, Ethan T. A.; Pedroarena, James R.; McGinnis, Tristan M.; Jarvo, Elizabeth R.

doi:10.1021/acs.orglett.4c02022

Org. Lett.

2024

DOI: 10.1021/acs.orglett.4c02022

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Sacrificial Anode-Free Electrochemical Cross-Electrophile Coupling of 1,3-Diol Derivatives to Form Aliphatic and Aryl Cyclopropanes

Nadia Hirbawi,

Ethan T. A. Raffman,

James R. Pedroarena

et al.

Abstract: Cross-electrophile coupling reactions that forge C(sp 3 )−C(sp 3 ) bonds are strategic methods for the synthesis of molecules with high F(sp 3 ), yet very few employ electrochemical conditions as the necessary reductant. Herein, we report an electrochemical intramolecular cross-electrophile coupling reaction of 1,3-diol derivatives to access aliphatic and aryl cyclopropanes, including spirocyclic and fused bicyclic cyclopropanes. The scalable electrochemical cross-electrophile coupling (eXEC) reaction employs … Show more

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Cited by 2 publications

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Cross‐Electrophile Couplings (XECs) between Similar Electrophile Reagents

Lei,

Yu,

2024

Chin. J. Chem.

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Comprehensive SummaryCross‐electrophile couplings (XEC), a crucial subset of cross‐coupling reactions, center on the formation of robust C—C bonds through the union of two electrophiles. Usually, such reactions have primarily been catalyzed by transition metals. However, with the steady advancements in photochemical and electrochemical technologies, XEC reactions have significantly progressed and broadened their scope, allowing for the utilization of a wider array of tolerable functional groups, thus revealing vast application prospects. This review aims to systematically summarize the current prevalent types of electrophiles and delve into their specific application examples within XEC reactions involving electrophiles with identical functional groups. Specifically, XECs between the same type of halides have received considerable attention, whereas carboxylic acids and alcohols are still in the early stages of investigation. Furthermore, certain other common electrophiles remain unexplored in this context. Moreover, this review underscores the remarkable contributions of photochemistry and electrochemistry in the field of XEC reactions, aiming to provide valuable insights and inspiration for researchers. Also, this review hopes to spark further interest in XEC reactions, thereby fueling the continuous development and advancement of this exciting area of research. Key ScientistsSince the 1960s, advancements in the XEC reaction have been substantial, driven primarily by the application of transition metal catalysts. In this area, many distinguished scientists have contributed their wisdom and efforts. Particularly noteworthy is that, during the systematic study of XEC reactions with the identical functional groups, in 2016, MacMillan achieved a photocatalytic XEC reaction between aryl bromides and alkyl bromides; in 2020, Weix successfully realized a nickel‐catalyzed XEC reaction between aryl chlorides and alkyl chlorides. Concurrently, contributions from researchers such as Mei, Wolf, Sevov, Lin, Shen, Browne, Zhang, and Qiu have expanded the scope of XEC reactions to various halides. By 2022, MacMillan and Baran achieved a significant milestone in the XEC between carboxylic acids, further broadening the scope of research in this area. Also, advancements in the XEC of alcohols have been noted, with researchers including Weix, Lian, Tu, and Stahl conducting pioneering work and successfully executing the XEC of protective groups. It is foreseen that the ongoing research endeavors will primarily concentrate on the expansion of diverse electrophiles.

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Cross‐Electrophile Couplings (XECs) between Similar Electrophile Reagents

Lei,

Yu,

2024

Chin. J. Chem.

View full text Add to dashboard Cite

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Electrochemical Cyclopropanation of 1,3-Dialkyl Bromides

Charvet,

Jacob,

Dietsch

et al. 2024

Org. Process Res. Dev.

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An electrochemical synthesis of mono-and 1,1-disubstituted cyclopropanes is demonstrated. Starting from readily available 1,3-dialkyl bromides, this method hinges on the integration of a sacrificial reductant alongside cost-effective cathode and anode materials. The refined approach eliminates the necessity for a divided cell and the use of hazardous or costly electrodes, thereby streamlining the transition of this protocol to a continuous flow system. In addition, an alternative protocol that utilizes a simple sacrificial anode is also described.

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Sacrificial Anode-Free Electrochemical Cross-Electrophile Coupling of 1,3-Diol Derivatives to Form Aliphatic and Aryl Cyclopropanes

Cited by 2 publications

References 71 publications

Cross‐Electrophile Couplings (XECs) between Similar Electrophile Reagents

Cross‐Electrophile Couplings (XECs) between Similar Electrophile Reagents

Electrochemical Cyclopropanation of 1,3-Dialkyl Bromides

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