A study of the reactivity of transition metal acyl enolates, in particular enolates of a chiral iron acyl complex, CpFe(CO)(PPh(,3))(COCH(,3)), has been undertaken. Concurrent with the above study has been the study of methods for the recovery of functionalized transition metal acyl ligands after enolate reaction. These recovered acyl ligands were found to have a defined relative stereochemistry at new chiral centers formed under the chiral iron atom's influence. A survey of reactivity with a variety of electrophiles was undertaken for a variety of transition metal acyl enolates. The types of reactions encompassed included enolate alkylations, stereoselective aldol and imine condensations, and condensations wtih nitrones and epoxides. The positively charged counterion associated with a transition metal acyl enolate was found to influence both the reactivity and stereoselectivity of the enolate in its reactions with prochiral substrates. The acyl ligands in transition metal acyl enolate alkylation products could be cleaved to esters, the aldol products cleaved to beta-hydroxy esters, and the imine condensation products converted into beta-lactams. A conjugate addition/alkylation sequence involving chiral alpha, beta unsaturated iron acyl complexes was also discovered. In this reaction, two new chiral centers were formed stereoselectively under the influence of the chiral iron in one reaction. The elaborated acyl ligands in these complexes could then be easily convered into single diastereomers of cis-disubstituted beta-lactams when primary amine anions were used for the conjugate addition, or erythro carboxylic acids when alkyl lithiums were used for the conjugate addition. / Source: Dissertation Abstracts International, Volume: 46-08, Section: B, page: 2674. / Thesis (Ph.D.)--The Florida State University, 1985.
| Identifer | oai:union.ndltd.org:fsu.edu/oai:fsu.digital.flvc.org:fsu_75622 |
| Contributors | WELKER, MARK EUGENE., Florida State University |
| Source Sets | Florida State University |
| Detected Language | English |
| Type | Text |
| Format | 279 p. |
| Rights | On campus use only. |
| Relation | Dissertation Abstracts International |
Page generated in 0.0022 seconds