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

Authors

Do W. Lee, Marquette UniversityFollow
Charles Felix Manful, Marquette University
Jayapal Reddy Gone, Marquette University
Yuzhi Ma, Marquette University
William Donaldson, Marquette UniversityFollow

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

Accepted version. Tetrahedron, Vol. 72, No. 5 (February 4, 2016): 753-759. DOI. © 2016 Elsevier. Used with permission.

Recommended Citation

Lee, Do W.; Manful, Charles Felix; Gone, Jayapal Reddy; Ma, Yuzhi; and Donaldson, William, "Reactivity of Acyclic (pentadienyl)iron(1+) Cations with Phosphonate Stabilized Nucleophiles: Application to the Synthesis of Oxygenated Metabolites of Carvone" (2016). Chemistry Faculty Research and Publications. 569.
https://epublications.marquette.edu/chem_fac/569