# Fluoride‐Transfer Asymmetric Allylic Alkylation Enables Regiodivergent, Stereoselective Cross‐Electrophile Coupling

**Authors:** Jordi Duran, Vyali Georgian Moldoveanu, Claudia Barroso, Geraldo Augusto Pereira, Bart Limburg, Xavier Companyó

PMC · DOI: 10.1002/anie.202520513 · Angewandte Chemie (International Ed. in English) · 2025-11-22

## TL;DR

This paper introduces a new chemical reaction method that efficiently builds carbon-carbon bonds with high selectivity and atom economy.

## Contribution

A fluoride-transfer asymmetric allylic alkylation method with full atom economy and regiodivergent cross-electrophile coupling.

## Key findings

- All reagent atoms are incorporated into the final products, achieving full atom economy.
- The method enables regiodivergent and stereoselective cross-electrophile coupling of allyl fluorides and gem-difluoroalkenes.
- Provides a catalyst-controlled access to trifluoromethylated homoallylic compounds.

## Abstract

Asymmetric allylic alkylation (AAA) is a widely used strategy for stereoselective formation of C─C bonds. Yet, conventional methods often exhibit poor atom economy as the leaving group is generally wasted. Herein, we report a fluoride‐transfer asymmetric allylic alkylation (AAA) in which all the atoms of the reagents are incorporated into the final products. The catalytic platform enables regiodivergent, stereoselective cross‐electrophile coupling of allyl fluorides and gem‐difluoroalkenes, where the regiochemical outcome is directed by the selective catalytic activation of one or the other electrophilic partner. The resulting atom‐efficient AAA protocol provides a regiocontrollable access to homoallylic trifluoromethylated compounds from a common set of electrophilic starting materials.

We report a fluoride‐transfer asymmetric allylic alkylation (AAA) in which all reagent atoms, including the leaving group, are incorporated into the products. This atom‐efficient AAA protocol enables the cross‐electrophile coupling of allyl fluorides and gem‐difluoroalkenes, providing a catalyst‐controlled, regiodivergent, and stereoselective access to trifluoromethylated homoallylic scaffolds.

## Linked entities

- **Chemicals:** fluoride (PubChem CID 28179)

## Full-text entities

- **Chemicals:** Fluoride (MESH:D005459), allyl fluorides (-), C (MESH:D002244)

## Full text

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## Figures

5 figures with captions in the complete paper: https://tomesphere.com/paper/PMC12790306/full.md

## References

108 references — full list in the complete paper: https://tomesphere.com/paper/PMC12790306/full.md

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Source: https://tomesphere.com/paper/PMC12790306