Iron-mediated allylic alkylation reactions.

Abstract

In this work it will be shown that Fe(CO)$\sb2$(NO)$\sb2$ mediated allylic alkylation reactions proceed via an intermediate which is neither an $\eta\sp3$-allyliron complex nor an $\eta\sp2$-allyliron complex. Rather, (Fe(CO)(NO)$\sb2$DMM)$\sp-$Na$\sp+$ has been identified as the catalytic intermediate. This provides the first evidence of an interaction between the nucleophile and the metallic center in reactions involving iron nitrosyl complexes. The study of the Fe(CO)$\sb3$(NO)$\sp-$Na$\sp+$, geranyl acetate, and NaDMM system was studied in order to elucidate the catalytically active species. Although it was determined that Fe(CO)$\sb3$(NO)$\sp-$Na$\sp+$ served as the precursor of a catalytic species X, the nature of X remains unknown.