Asymmetric pentafulvene carbometalation-access to enantiopure titanocene dichlorides of biological relevance
Unprecedented asymmetric copper-catalyzed addition of ZnEt2 (ZnBu2) to the exocyclic C[DOUBLE BOND]C bond of pentafulvenes C5H4([DOUBLE BOND]CHAr) (Ar=2-MeOPh and related species) results in enantiomerically enriched (up to 93:7 e.r.) cyclopentadienyl ligands (C5H4CHEtAr; abbreviated CpR). Copper ca...
| Main Authors: | , , , |
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| Format: | Article |
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Wiley
2015
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| Online Access: | https://eprints.nottingham.ac.uk/37572/ |
| _version_ | 1848795486945804288 |
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| author | Cini, Melchior Bradshaw, Tracey D. Woodward, Simon Lewis, William |
| author_facet | Cini, Melchior Bradshaw, Tracey D. Woodward, Simon Lewis, William |
| author_sort | Cini, Melchior |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | Unprecedented asymmetric copper-catalyzed addition of ZnEt2 (ZnBu2) to the exocyclic C[DOUBLE BOND]C bond of pentafulvenes C5H4([DOUBLE BOND]CHAr) (Ar=2-MeOPh and related species) results in enantiomerically enriched (up to 93:7 e.r.) cyclopentadienyl ligands (C5H4CHEtAr; abbreviated CpR). Copper catalyst promotion with both chiral phosphoramidite ligands and a phosphate additive is vital in realizing both acceptable enantioselectivities and reaction rates. Enantiomeric CpR2TiCl2 complexes have been prepared; the (S,S) isomer is twice as active towards pancreatic, breast, and colon cancer cell lines as its (R,R) enantiomer at 24 h. |
| first_indexed | 2025-11-14T19:32:52Z |
| format | Article |
| id | nottingham-37572 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:32:52Z |
| publishDate | 2015 |
| publisher | Wiley |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-375722020-05-04T17:22:53Z https://eprints.nottingham.ac.uk/37572/ Asymmetric pentafulvene carbometalation-access to enantiopure titanocene dichlorides of biological relevance Cini, Melchior Bradshaw, Tracey D. Woodward, Simon Lewis, William Unprecedented asymmetric copper-catalyzed addition of ZnEt2 (ZnBu2) to the exocyclic C[DOUBLE BOND]C bond of pentafulvenes C5H4([DOUBLE BOND]CHAr) (Ar=2-MeOPh and related species) results in enantiomerically enriched (up to 93:7 e.r.) cyclopentadienyl ligands (C5H4CHEtAr; abbreviated CpR). Copper catalyst promotion with both chiral phosphoramidite ligands and a phosphate additive is vital in realizing both acceptable enantioselectivities and reaction rates. Enantiomeric CpR2TiCl2 complexes have been prepared; the (S,S) isomer is twice as active towards pancreatic, breast, and colon cancer cell lines as its (R,R) enantiomer at 24 h. Wiley 2015-11-16 Article PeerReviewed Cini, Melchior, Bradshaw, Tracey D., Woodward, Simon and Lewis, William (2015) Asymmetric pentafulvene carbometalation-access to enantiopure titanocene dichlorides of biological relevance. Angewandte Chemie International Edition, 54 (47). pp. 14179-14182. ISSN 1521-3773 http://onlinelibrary.wiley.com/doi/10.1002/anie.201508034/full doi:10.1002/anie.201508034 doi:10.1002/anie.201508034 |
| spellingShingle | Cini, Melchior Bradshaw, Tracey D. Woodward, Simon Lewis, William Asymmetric pentafulvene carbometalation-access to enantiopure titanocene dichlorides of biological relevance |
| title | Asymmetric pentafulvene carbometalation-access to enantiopure titanocene dichlorides of biological relevance |
| title_full | Asymmetric pentafulvene carbometalation-access to enantiopure titanocene dichlorides of biological relevance |
| title_fullStr | Asymmetric pentafulvene carbometalation-access to enantiopure titanocene dichlorides of biological relevance |
| title_full_unstemmed | Asymmetric pentafulvene carbometalation-access to enantiopure titanocene dichlorides of biological relevance |
| title_short | Asymmetric pentafulvene carbometalation-access to enantiopure titanocene dichlorides of biological relevance |
| title_sort | asymmetric pentafulvene carbometalation-access to enantiopure titanocene dichlorides of biological relevance |
| url | https://eprints.nottingham.ac.uk/37572/ https://eprints.nottingham.ac.uk/37572/ https://eprints.nottingham.ac.uk/37572/ |