Complexation Strategies towards Challenging Group 9 Metal Cyclopentadienyl Scaffolds

Cyclopentadienyl (Cp) metal complexes and their chiral counterparts (CpX) have enabled the development of challenging C-H activation transformations. While major progresses were made in developing new chiral CpX complexes and exploring their reactivity, the discovery of new achiral Cps remained underexplored. Monosubstituted Cps due to their stability issue and difficult synthesis have been particularly overlooked as catalyst in C-H functionalization reactions. Although recent efforts have been made on developing mild and broadly applicable complexation strategies, a general highly face-selective complexation of non C2-symmetric ligands remains so far elusive. A novel oxygen- and water-tolerant approach to monosubstituted Cp metal complexes under mild conditions is disclosed in this thesis. The complexation method relies on bench stable fulvene and metal precursors in combination with a broad range of carbon-, oxygen- and nitrogen nucleophiles. The under-representation of chiral C1-symmetric CpX is explained by the absence of reliable complexation strategy to access them. In this optic, we disclose in this thesis, a general enantiospecific complexation from point chiral cyclopentadienes. This method allows for a fast construction of a library of new planar chiral complexes that display promising reactivity and selectivity in various group 9 metal-catalyzed transformations.