Title

Reactivity of Acyclic (pentadienyl)iron(1+) Cations with Phosphonate Stabilized Nucleophiles: Application to the Synthesis of Oxygenated Metabolites of Carvone

Document Type

Article

Language

eng

Format of Original

7 p.

Publication Date

2-4-2016

Publisher

Elsevier

Source Publication

Tetrahedron

Source ISSN

0040-4020

Abstract

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.

Comments

Tetrahedron, Vol. 72, No. 5 (February 4, 2016): 753-759. DOI.