Asymmetric synthesis via iron acyl complexes
<p>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 [(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)(PPh&l...
| Main Authors: | , |
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| Format: | Thesis |
| Language: | English |
| Published: |
1986
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| _version_ | 1797069366185951232 |
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| author | Walker, J Walker, Jonathan |
| author2 | Davies, S |
| author_facet | Davies, S Walker, J Walker, Jonathan |
| author_sort | Walker, J |
| collection | OXFORD |
| description | <p>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 [(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)(PPh<sub>3</sub>)].</p><p> Chapter 1 briefly reviews the use of chiral auxiliaries in asymmetric synthesis.</p><p>Chapter 2 discusses the conformation of [(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)(PPh<sub>3</sub>)COCH<sub>3</sub>] with reference to its X-ray crystal structure. A method for determining the absolute configuration of (+)- and (-)-[(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)(PPh<sub>3</sub>)COCH<sub>3</sub>] is described as well as methods for determining their optical purities.</p><p>Chapter 3 describes methods for the preparation of α,β-unsaturated acyl complexes. The Peterson reaction between the enolate derived from [(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)(PPh<sub>3</sub>) COCH<sub>2</sub> Si (CH<sub>3</sub>)<sub>3</sub>] and aldehydes gives complexes of the type [(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)(PPh<sub>3</sub>) 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 [η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)(PPh<sub>3</sub>)COC(R)=CH<sub>2</sub>] are similarly prepared from the corresponding β-methoxy acyl complexes. The conformations of E- and Z- [η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)(PPh<sub>3</sub>)COC(R)=CH<sub>2</sub>] are discussed with reference to the X-ray crystal structures of the β-methoxy substituted complexes.</p><p>See thesis pdf for remainder of abstract</p> |
| first_indexed | 2024-03-06T22:23:22Z |
| format | Thesis |
| id | oxford-uuid:55cfc478-5868-474f-9d2b-532218ec6fd6 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T22:23:22Z |
| publishDate | 1986 |
| record_format | dspace |
| spelling | oxford-uuid:55cfc478-5868-474f-9d2b-532218ec6fd62022-03-26T16:46:40ZAsymmetric synthesis via iron acyl complexesThesishttp://purl.org/coar/resource_type/c_db06uuid:55cfc478-5868-474f-9d2b-532218ec6fd6Asymmetric synthesisIron compoundsStereochemistryAcyl halidesChiralityEnglishPolonsky Theses Digitisation Project1986Walker, JWalker, JonathanDavies, SDavies, S<p>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 [(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)(PPh<sub>3</sub>)].</p><p> Chapter 1 briefly reviews the use of chiral auxiliaries in asymmetric synthesis.</p><p>Chapter 2 discusses the conformation of [(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)(PPh<sub>3</sub>)COCH<sub>3</sub>] with reference to its X-ray crystal structure. A method for determining the absolute configuration of (+)- and (-)-[(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)(PPh<sub>3</sub>)COCH<sub>3</sub>] is described as well as methods for determining their optical purities.</p><p>Chapter 3 describes methods for the preparation of α,β-unsaturated acyl complexes. The Peterson reaction between the enolate derived from [(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)(PPh<sub>3</sub>) COCH<sub>2</sub> Si (CH<sub>3</sub>)<sub>3</sub>] and aldehydes gives complexes of the type [(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)(PPh<sub>3</sub>) 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 [η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)(PPh<sub>3</sub>)COC(R)=CH<sub>2</sub>] are similarly prepared from the corresponding β-methoxy acyl complexes. The conformations of E- and Z- [η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)(PPh<sub>3</sub>)COC(R)=CH<sub>2</sub>] are discussed with reference to the X-ray crystal structures of the β-methoxy substituted complexes.</p><p>See thesis pdf for remainder of abstract</p> |
| spellingShingle | Asymmetric synthesis Iron compounds Stereochemistry Acyl halides Chirality Walker, J Walker, Jonathan Asymmetric synthesis via iron acyl complexes |
| title | Asymmetric synthesis via iron acyl complexes |
| title_full | Asymmetric synthesis via iron acyl complexes |
| title_fullStr | Asymmetric synthesis via iron acyl complexes |
| title_full_unstemmed | Asymmetric synthesis via iron acyl complexes |
| title_short | Asymmetric synthesis via iron acyl complexes |
| title_sort | asymmetric synthesis via iron acyl complexes |
| topic | Asymmetric synthesis Iron compounds Stereochemistry Acyl halides Chirality |
| work_keys_str_mv | AT walkerj asymmetricsynthesisviaironacylcomplexes AT walkerjonathan asymmetricsynthesisviaironacylcomplexes |