@article { , title = {Asymmetric pentafulvene carbometalation-access to enantiopure titanocene dichlorides of biological relevance}, abstract = {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.}, doi = {10.1002/anie.201508034}, eissn = {1521-3773}, issn = {1433-7851}, issue = {47}, journal = {Angewandte Chemie International Edition}, publicationstatus = {Published}, publisher = {Wiley}, url = {https://nottingham-repository.worktribe.com/output/766531}, volume = {54}, year = {2015}, author = {Cini, Melchior and Bradshaw, Tracey D. and Woodward, Simon and Lewis, William} }