American Chemical Society
om0c00307_si_001.pdf (5.34 MB)

endo-Selective Iron Catalysts for Intramolecular Alkyne Hydrofunctionalization

Download (5.34 MB)
journal contribution
posted on 2020-07-06, 15:34 authored by Benjamin J. Bridge, Paul D. Boyle, Johanna M. Blacquiere
Metal–ligand cooperative iron complexes of the type [Fe­(Cp*)­(PR2NPh2)­(MeCN)]­PF6 (R = Cy, Ph) were synthesized and characterized. Both derivatives were active toward the intramolecular hydroamination of 2-ethynylaniline and hydroalkoxylation of 2-ethynylbenzyl alcohol. In the latter case, only the six-membered endo heterocycle isochromene was observed, which suggests that the alkyne is activated by a vinylidene mechanism. The reaction of [Fe­(Cp*)­(PCy2NPh2)­(MeCN)]­PF6 with phenylacetylene indeed afforded a complex that was characterized as a vinylidene, which implicates an analogous intermediate in the hydrofunctionalization mechanism.