The synthesis of enantiomerically pure titanocenes is limited to cases with enantiomerically pure substituents at the cyclopentadienyl ligands and to ansa-titanocenes. For the latter complexes, the use of achiral ligands requires a resolution of enantiomers and frequently also a separation of the diastereoisomers obtained after metalation. Here, we introduce a new synthetic method that relies on the use of enantiomerically pure camphorsulfonate (CSA) ligands as control elements for the absolute and relative configuration of titanocene complexes. Starting from the conformationally flexible (RC H ) TiCl , the desired conformationally locked and hence enantio- and diastereomerically pure complexes (RC H ) Ti(CSA) are obtained in just two steps. According to X-ray crystallography the (RC H ) Ti fragment is essentially C -symmetric and nuclear magnetic resonance displays overall C -symmetry. We applied density functional theory methods to unravel the dynamics of the complexes and the mechanisms and selectivities of their formation.
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http://dx.doi.org/10.1002/chem.202301645 | DOI Listing |
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