Nucleophilic Addition to (3-Methylpentadienyl)iron(1+) Cations: Counterion Control of Regioselectivity; Application to the Enantioselective Synthesis of 4,5-Disubstituted Cyclohexenones

Authors

Subhabrata Chaudhury, Marquette University
William Donaldson, Marquette UniversityFollow

Document Type

Article

Language

eng

Format of Original

2 p.

Publication Date

2006

Publisher

American Chemical Society

Source Publication

Journal of the American Chemical Society

Source ISSN

0002-7863

Original Item ID

DOI: 10.1021/ja055668y

Abstract

The regioselectivity of malonate addition to (3-methylpentadienyl)Fe(CO)₃⁺ is controlled by the malonate−counterion association. The Li⁺ salt of malonate proceeds via C1 nucleophilic attack to afford the 1,3Z-diene complex 4a, while reaction of highly dissociated ion pair (i.e., Na⁺ or Li⁺/12-crown-4) salt proceeds at the C2 internal carbon to eventually afford cyclohexenone products 6. Reaction of 1a with the sodium salt of bis(8-phenylmenthyl)malonate proceeds with excellent diastereocontrol to afford a single diastereomeric cyclohexenone.

Comments

Accepted version. Journal of the American Chemical Society, Vol. 128. No. 18 (2006) pp 5984-5985. DOI. © 2006 American Chemical Society. Used with permission.

Recommended Citation

Chaudhury, Subhabrata and Donaldson, William, "Nucleophilic Addition to (3-Methylpentadienyl)iron(1+) Cations: Counterion Control of Regioselectivity; Application to the Enantioselective Synthesis of 4,5-Disubstituted Cyclohexenones" (2006). Chemistry Faculty Research and Publications. 52.
https://epublications.marquette.edu/chem_fac/52