Unveiling the Power of Tunable RXZnCH2I Carbenoids for the Cyclopropanation of Olefins

Abstract

Cyclopropanes are both valuable building blocks in synthetic chemistry and important functional moieties existing in natural products and biologically active molecules. The Simmons–Smith cyclopropanation has become a very useful and reliable method for the synthesis of cyclopropanes from olefins. Aiming at the development of tunable and highly reactive zinc carbenoids, Shi and coworkers proposed an effective strategy for the generation of zinc carbenoids RXZnCH₂I by reacting RXH with an appropriate organozinc reagent, which allows tuning the reactivity of RXZnCH₂I reagents simply by changing the modifier RXH. This type of carbenoid reagent- is known as Shi carbenoid or reagent and has been found to be highly effective for each type of olefins, which attracts intensive attention and results in numerous successful applications in the synthesis of complex molecules, as well as important cyclopropane building blocks. Significantly, the asymmetric Simmons–Smith cyclopropanation of unfunctionalized olefins has also been achieved using a chiral modifier.

Keywords

Cyclopropane - Simmons–Smith reaction - Zinc carbenoids - Shi carbenoids - Asymmetric cyclopropanation

Publikationsverlauf

Eingereicht: 17. September 2025

Angenommen nach Revision: 27. Oktober 2025

Accepted Manuscript online:
27. Oktober 2025

Artikel online veröffentlicht:
26. November 2025

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