Stereocontrolled Access to ( Z )‐Heteroatom‐Substituted Fluoroalkenes Through Fluorine‐Directed, Hydrogen‐Bond‐Assisted Elimination
Zhaoxuan Xu, Zimeng Li, Songsong Xu, Qilong ShenABSTRACT
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.