Organocatalytic Enantioselective Nucleophilic Alkynylation of Allyl Fluorides Affording Chiral Skipped Ene-ynes

Asymmetric methods for preparation of chiral alkynyl‐containing compounds are in extremely high demand in many sectors of chemical research. In this work, we report the discovery of a general organocatalytic enantioselective alkynylation based on the idea of Si/F activation of the allylic C−F bond. This approach features reasonably broad substrate scope, functional group tolerance, and relatively neutral, mild, and operationally convenient reaction conditions; all of which bode well for the synthetic value of the discovered method. In particular, this method provides unique chiral skipped 1,4‐ene‐ynes having two kinds of versatile functional groups. Nicht konjugiert, dafür chiral: Eine organokatalytische enantioselektive Alkinylierung verläuft unter Si/F‐Aktivierung der allylischen C‐F‐Bindung. Die Reaktion eignet sich für eine Reihe von Substraten, ist mit funktionellen Gruppen verträglich und ist unter milden, neutralen Bedingungen bequem auszuführen.