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Angewandte Chemie International Edition· 2026Q1

Stereocontrolled Access to ( Z )‐Heteroatom‐Substituted Fluoroalkenes Through Fluorine‐Directed, Hydrogen‐Bond‐Assisted Elimination

Zhaoxuan Xu, Zimeng Li, Songsong Xu, Qilong Shen

Short summary

A new method synthesizes (Z)-1,2-heteroatom-substituted monofluoroethylenes via Michael addition to a fluorovinyl sulfonium ylide, followed by E2 elimination, achieving Z-selectivity through an intramolecular hydrogen bond.

AI-generated from the title and abstract; the full text is not read.

Key points

  • Developed a general method for stereoselective synthesis of (Z)-1,2-heteroatom-substituted monofluoroethylenes.
  • Reaction proceeds via Michael addition of N-, P-, and S-nucleophiles to a fluorovinyl sulfonium ylide, followed by E2 elimination.
  • Achieves Z-selectivity, with mechanistic studies pointing to an intramolecular hydrogen bond in the intermediate as the key stereocontrolling factor.
  • Demonstrates broad functional group tolerance and potential for late-stage functionalization of bioactive molecules and oligopeptides.

AI-generated from the title and abstract; the full text is not read.

Abstract

A general method for the stereocontrolled synthesis of (Z)-1,2-heteroatom-substituted monofluoroethylenes is described. The reaction proceeds via the Michael addition of N-, P-, and S-centered nucleophiles to 1-fluorovinyl sulfonium ylide (Ylide-VF) under mild conditions, followed by an E2 process. This general protocol exhibits broad functional group tolerance and significant application potential, as demonstrated by the late-stage functionalization of bioactive molecules and oligopeptides. Mechanistic investigations reveal that an intramolecular hydrogen bond within the Michael addition intermediate is the key stereocontrolling element, dictating the observed Z-selectivity.

The authors' abstract, as published at the source. Angewandte Chemie International Edition, 2026 · DOI ↗

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Field: Pharmaceutical Science

Pharmaceutical SciencePharmacology, Toxicology and Pharmaceutics