Photoredox/Nickel Dual Catalysis Enables the Synthesis of Alkyl Cyclopropanes via C(sp³)–C(sp³) Cross Electrophile Coupling of Unactivated Alkyl Electrophiles

Abstract

A facile synthesis of mono-, 1,1-and 1,2disubstituted cyclopropanes via visible light-mediated photoredox/nickel dual catalysis is demonstrated. The challenging intramolecular C(sp 3 )−C(sp 3 ) cross-electrophile coupling of readily available unactivated 1,3-dialkyl electrophiles was performed under mild conditions that allowed traditionally reactive functional groups to be included. Mechanistic inspection and control experiments revealed the importance of dual catalysis and that the reaction proceeds via a stepwise oxidative addition followed by an intramolecular S N 2 reaction.

Construction of 1,2,4-triazole-fused heterocycles via an amine oxidase-inspired catalyst

“…30,33 To further demonstrate the synthetic applicability of the heteroarene triazoles, 3aq was successfully used as a bidentate ligand in a photoredox/nickel-catalyzed cross-electrophile coupling reaction for the synthesis of alkyl cyclopropanes (Scheme 2d). 34…”

Visible Light‐Mediated Cyclopropanation: Recent Progress

“…Maji et al described a photoredox/nickel dual catalyzed cyclopropanation for the synthesis of mono-, 1,1-and 1,2disubstituted cyclopropanes (Scheme 28). [68] This strategy realized the intramolecular cross-electrophilic coupling reactions utilizing un-activated 1,3-dialkyl electrophilic reagents as substrates. Throughout the photocatalytic cycle, triethanolamine acts as an organic electron donor, transferring electrons to the excited state of the photosensitizer to facilitate the overall nickel-catalyzed cross-electrophilic coupling.…”

Zinc-Mediated Transformation of 1,3-Diols to Cyclopropanes for Late-Stage Modification of Natural Products and Medicinal Agents

“…We set out to establish a method that would achieve late-stage synthesis of cyclopropanes from complex 1,3-diols employing mild reagents. On the basis of our prior work in the development of nickel-catalyzed intramolecular cross-electrophile coupling (XEC) reactions of 1,3-dimesylates, we hypothesized that 1,3-dimesylates would undergo a reducing metal-mediated XEC reaction to form cyclopropanes. − In this work, we report a zinc-mediated conversion of 1,3-dimesylates to cyclopropanes and demonstrate this reaction on several natural product and medicinal agent cores, including a series of statins.…”