Hydrogen Atom Transfer (HAT)-Mediated Remote Desaturation Enabled by Fe/Cr–H Cooperative Catalysis

An iron/chromium system (Fe(OAc)2, CpCr(CO)3H) catalyzes the preparation of β,γ- or γ,δ-unsaturated amides from 1,4,2-dioxazol-5-ones. An acyl nitrenoid iron complex seems likely to be responsible for C–H activation. A cascade of three H• transfer steps appears to be involved: (i) the abstraction of H• from a remote C–H bond by the nitrenoid N, (ii) the transfer of H• from Cr to N, and (iii) the abstraction of H• from a radical substituent by the Cr•. The observed kinetic isotope effects are consistent with the proposed mechanism if nitrenoid formation is the rate-determining step. The Fe/Cr catalysts can also desaturate substituted 1,4,2-dioxazol-5-ones to 3,5-dienamides.