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Title: Asymmetric synthesis via iron acyl complexes
Author: Walker, Jonathan Charles
ISNI:       0000 0001 3553 8589
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 1986
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This thesis describes the applications to asymmetric synthesis of the highly diastereoselective carbon-carbon bond forming reactions of α,β-unsaturated acyl ligands bound to the chiral iron auxiliary [(η5-C5H5)Fe(CO)(PPh3)]. Chapter 1 briefly reviews the use of chiral auxiliaries in asymmetric synthesis. Chapter 2 discusses the conformation of [(η5-C5H5)Fe(CO)(PPh3)COCH3] with reference to its X-ray crystal structure. A method for determining the absolute configuration of (+)- and (-)-[(η5-C5H5)Fe(CO)(PPh3)COCH3] is described as well as methods for determining their optical purities. Chapter 3 describes methods for the preparation of α,β-unsaturated acyl complexes. The Peterson reaction between the enolate derived from [(η5-C5H5)Fe(CO)(PPh3) COCH2 Si (CH3)3] and aldehydes gives complexes of the type [(η5-C5H5)Fe(CO)(PPh3) COCH=CHR] as mixtures of E and Z isomers. Sodium hydride-induced elimination of methanol from either diastereoisomer of the corresponding β-methoxy acyl complex gives the E isomer stereo-selectively. Complexes of the type [η5-C5H5)Fe(CO)(PPh3)COC(R)=CH2] are similarly prepared from the corresponding β-methoxy acyl complexes. The conformations of E- and Z- [η5-C5H5)Fe(CO)(PPh3)COC(R)=CH2] are discussed with reference to the X-ray crystal structures of the β-methoxy substituted complexes.
Supervisor: Davies, Stephen G. Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Asymmetric synthesis ; Iron compounds ; Acyl halides ; Chirality ; Stereochemistry