Steric-switched defluorofunctionalization selectivity: controlled synthesis of monofluoroalkene-masked medium-sized heterocyclic lactams and lactones

The steric-switched ipso-defluoroamination-triggered and ipso-defluorooxylation-triggered cyclization of(trifluoromethyl)alkenes with amino alcohols and diamines are achieved under mild conditions. This regioselective strategy distinguishes the different nucleophilic heteroatom sites in amino alcohols and unsymmetric diamines by the sequential defluorinative functionalization of two C(sp^(3))–F bonds in a CF_(3) group. Various attractive monofluoroalkene-masked medium-sized heterocyclic lactams and lactones are obtained in moderate to excellent yields. Simple derivation of these masked-heterocycles efficiently affords useful skeletons of lactams, lactones, and 1,4-oxazepanes in a single diastereoisomer. Mechanism studies indicate that a unique sequential ipso-/γ-selective defluorinative functionalization pathway is involved in these transformations.

Bond energy enabled amine distinguishing strategy:chemo-,regioselective 1,3-diamination of(trifluoromethyl)alkenes with different amines by two C(sp^(3))-F bond cleavages

The methods to distinguish between amines are rarely investigated.In this article,a bond energy enabled amine distinguishing strategy is reported.With(trifluoromethyl)alkenes as linchpins,a chemo-,regio-selective three-component defluorinative 1,3-diamination reaction with two different amine nucleophiles was achieved.