Physical Sciences and Mathematics Commons^™

Reactivity Of Acyclic (Pentadienyl)Iron(1+) Cations With Phosphonate Stabilized Nucleophiles: Application To The Synthesis Of Oxygenated Metabolites Of Carvone, Do W. Lee, Charles Felix Manful, Jayapal Reddy Gone, Yuzhi Ma, William Donaldson

Chemistry Faculty Research and Publications

The addition of phosphonate stabilized carbon nucleophiles to acyclic (pentadienyl)iron(1+) cations proceeds predominantly at an internal carbon to afford (pentenediyl)iron complexes. Those complexes bearing an electron withdrawing group at the σ-bound carbon (i.e., 13/14) are stable and isolable, while complexes which do not contain an electron withdrawing group at the σ-bound carbon undergo CO insertion, reductive elimination and conjugation of the double bond to afford cyclohexenone products (21/22). Deprotonation of the phosphonate 13/14 or 21 and reaction with paraformaldehyde affords the olefinated products. This methodology was utilized to prepare oxygenated carvone metabolites (±)-25 and (±)-26.