KINETIC RESOLUTION OF THE CHIRAL IRON ACETYL COMPLEXES [FE(CO)(ETA(5)-C5H5)-(L)COCH3] [L=PPH(3), P(P-TOLYL)(3)] VIA ALDOL REACTIONS WITH CAMPHOR
The chiral iron acetyl complexes [Fe(CO)(η5-C 5H5)(L)COCH3] [L = PPh3, P(p-tolyl)3] have been kinetically resolved via aldol reactions involving their derived lithium enolates and camphor in the presence of lithium chloride. With (1R)-(+)-camphor the faster reacting iron acetyl enantiomer had the (S...
| Hauptverfasser: | , , , , , , , |
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| Format: | Journal article |
| Sprache: | English |
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1994
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| _version_ | 1826279029583380480 |
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| author | Casegreen, S Costello, J Davies, S Heaton, N Hedgecock, C Humphreys, V Metzler, M Prime, J |
| author_facet | Casegreen, S Costello, J Davies, S Heaton, N Hedgecock, C Humphreys, V Metzler, M Prime, J |
| author_sort | Casegreen, S |
| collection | OXFORD |
| description | The chiral iron acetyl complexes [Fe(CO)(η5-C 5H5)(L)COCH3] [L = PPh3, P(p-tolyl)3] have been kinetically resolved via aldol reactions involving their derived lithium enolates and camphor in the presence of lithium chloride. With (1R)-(+)-camphor the faster reacting iron acetyl enantiomer had the (S)-configuration allowing the (R)-iron acetyls to be obtained after recovery of starting material and crystallisation. The corresponding (S)-iron acetyls can be obtained by a base-promoted reverse aldol reaction of the isolated products. A mechanistic rationale for the high enantiomeric discrimination is proposed which involves a chelation-controlled chair transition state with a disfavourable 1 -methyl to cyclopentadienyl interaction in the mismatched pairing. |
| first_indexed | 2024-03-06T23:52:44Z |
| format | Journal article |
| id | oxford-uuid:732a80c4-5205-4382-9a1f-7bc297dba241 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T23:52:44Z |
| publishDate | 1994 |
| record_format | dspace |
| spelling | oxford-uuid:732a80c4-5205-4382-9a1f-7bc297dba2412022-03-26T19:54:40ZKINETIC RESOLUTION OF THE CHIRAL IRON ACETYL COMPLEXES [FE(CO)(ETA(5)-C5H5)-(L)COCH3] [L=PPH(3), P(P-TOLYL)(3)] VIA ALDOL REACTIONS WITH CAMPHORJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:732a80c4-5205-4382-9a1f-7bc297dba241EnglishSymplectic Elements at Oxford1994Casegreen, SCostello, JDavies, SHeaton, NHedgecock, CHumphreys, VMetzler, MPrime, JThe chiral iron acetyl complexes [Fe(CO)(η5-C 5H5)(L)COCH3] [L = PPh3, P(p-tolyl)3] have been kinetically resolved via aldol reactions involving their derived lithium enolates and camphor in the presence of lithium chloride. With (1R)-(+)-camphor the faster reacting iron acetyl enantiomer had the (S)-configuration allowing the (R)-iron acetyls to be obtained after recovery of starting material and crystallisation. The corresponding (S)-iron acetyls can be obtained by a base-promoted reverse aldol reaction of the isolated products. A mechanistic rationale for the high enantiomeric discrimination is proposed which involves a chelation-controlled chair transition state with a disfavourable 1 -methyl to cyclopentadienyl interaction in the mismatched pairing. |
| spellingShingle | Casegreen, S Costello, J Davies, S Heaton, N Hedgecock, C Humphreys, V Metzler, M Prime, J KINETIC RESOLUTION OF THE CHIRAL IRON ACETYL COMPLEXES [FE(CO)(ETA(5)-C5H5)-(L)COCH3] [L=PPH(3), P(P-TOLYL)(3)] VIA ALDOL REACTIONS WITH CAMPHOR |
| title | KINETIC RESOLUTION OF THE CHIRAL IRON ACETYL COMPLEXES [FE(CO)(ETA(5)-C5H5)-(L)COCH3] [L=PPH(3), P(P-TOLYL)(3)] VIA ALDOL REACTIONS WITH CAMPHOR |
| title_full | KINETIC RESOLUTION OF THE CHIRAL IRON ACETYL COMPLEXES [FE(CO)(ETA(5)-C5H5)-(L)COCH3] [L=PPH(3), P(P-TOLYL)(3)] VIA ALDOL REACTIONS WITH CAMPHOR |
| title_fullStr | KINETIC RESOLUTION OF THE CHIRAL IRON ACETYL COMPLEXES [FE(CO)(ETA(5)-C5H5)-(L)COCH3] [L=PPH(3), P(P-TOLYL)(3)] VIA ALDOL REACTIONS WITH CAMPHOR |
| title_full_unstemmed | KINETIC RESOLUTION OF THE CHIRAL IRON ACETYL COMPLEXES [FE(CO)(ETA(5)-C5H5)-(L)COCH3] [L=PPH(3), P(P-TOLYL)(3)] VIA ALDOL REACTIONS WITH CAMPHOR |
| title_short | KINETIC RESOLUTION OF THE CHIRAL IRON ACETYL COMPLEXES [FE(CO)(ETA(5)-C5H5)-(L)COCH3] [L=PPH(3), P(P-TOLYL)(3)] VIA ALDOL REACTIONS WITH CAMPHOR |
| title_sort | kinetic resolution of the chiral iron acetyl complexes fe co eta 5 c5h5 l coch3 l pph 3 p p tolyl 3 via aldol reactions with camphor |
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