Reactivity of (bicyclo[5.1.0]octadienyl)iron(1+) cations: application to the synthesis of cis-2-(2'-carboxycyclopropyl)glycines.

The addition of carbon and heteroatom nucleophiles to (bicyclo[5.1.0]octadienyl)Fe(CO)(2)L(+) cations 5 or 8 (L = CO, PPh(3)) 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)(2)L (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 (RuCl(3)/NaIO(4)) 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).