Reactivity of (Bicyclo[5.1.0]octadienyl)iron(1+) Cations: Application to the Synthesis of cis-2-(2’-carboxycyclopropyl)glycines

Authors

Nathaniel J. Wallock, Marquette UniversityFollow
William A. Donaldson, Marquette UniversityFollow

Document Type

Article

Language

eng

Format of Original

11 p.

Publication Date

3-2004

Publisher

American Chemical Society

Source Publication

Journal of Organic Chemitry

Source ISSN

0022-3263

Original Item ID

DOI: 10.1021/jo030259a

Abstract

The addition of carbon and heteroatom nucleophiles to (bicyclo[5.1.0]octadienyl)Fe(CO)₂L⁺ cations 5 or 8 (L = CO, PPh₃) generally proceeds via attack at the dienyl terminus on the face of the ligand opposite to iron to generate 6-substituted (bicyclo[5.1.0]octa-2,4-diene)iron complexes (11 or 13). In certain cases, these products are unstable with respect to elimination of a proton and the nucleophilic substituent to afford (cyclooctatetraene)Fe(CO)₂L (4 or 7). Decomplexation of 13f, arising from addition of phthalimide to 8, gave N-(bicyclo[5.1.0]octa-3,5-dien-2-yl)phthalimide (19). Oxidative cleavage of 19 (RuCl₃/NaIO₄) followed by esterification gave the cyclopropane diester 22, which upon hydrolysis gave cis-2-(2‘-carboxycyclopropyl)glycine (CCG-III, 18) (eight steps from 4, 43% overall yield). This methodology was also utilized for preparation of stereospecifically deuterated CCG-III (d-18) and optically enriched (−)-18. Deprotonation of 22 resulted in cyclopropane ring opening to afford the benzoindolizidine (23).

Comments

Accepted version. Journal of Organic Chemistry, Volume 69, Number 9 (2004): 2997-3007. DOI. © 2004 American Chemical Society. Used with permission.

Recommended Citation

Wallock, Nathaniel J. and Donaldson, William A., "Reactivity of (Bicyclo[5.1.0]octadienyl)iron(1+) Cations: Application to the Synthesis of cis-2-(2’-carboxycyclopropyl)glycines" (2004). Chemistry Faculty Research and Publications. 79.
https://epublications.marquette.edu/chem_fac/79