Cyanomethyl anion transfer reagents for diastereoselective Corey–Chaykovsky cyclopropanation reactions

In this report, we describe an application of ethyl difluoroacetate‐substituted allylic sulfides in Doyle‐Kirmse rearrangement reactions that allow efficient access to valuable fluorinated small molecules with applications in total synthesis and drug discovery. A cheap and readily available rhodium catalyst or – in a metal‐free variant – visible light was used to generate a carbene intermediate to access rearrangement reactions in high yield.

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Catalytic Synthesis of Trifluoromethyl Cyclopropenes and Oligo‐Cyclopropenes

Tran

Hommelsheim

Yang

et al. 2020

Chemistry A European J

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The synthesis of trifluoromethylated cyclopropenes is often associated with important applications in drug discovery and functional materials. In this report, we describe the use of readily available chiral rhodium(II) catalysts for a highly efficient asymmetric cyclopropenation reaction of fluorinated donor–acceptor diazoalkanes with a broad variety of aliphatic and aromatic alkynes. Further studies highlight the unique reactivity of fluorinated donor–acceptor diazoalkanes in the synthesis of oligo‐cyclopropenes. Subsequent C−H functionalization of trifluoromethyl cyclopropenes furnishes densely substituted cyclopropene frameworks and also allows the alternative synthesis of bis‐cyclopropenes.

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Cyanomethyl anion transfer reagents for diastereoselective Corey–Chaykovsky cyclopropanation reactions

Abstract: A readily available and bench-stable cyanomethyl sulfonium salt was used in highly diastereoselective Corey-Chaykovsky cyclopropanation reactions of electron-poor olefins. This efficient method provides a rapid route to access densely functionalized cyclopropyl nitriles.

Cited by 8 publications

References 40 publications

Nitro Cyclopropanes: Synthesis and Applications

Nitro Cyclopropanes: Synthesis and Applications

Doyle‐Kirmse Rearrangement Reactions of Difluoroacetates

Catalytic Synthesis of Trifluoromethyl Cyclopropenes and Oligo‐Cyclopropenes

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