Design of Novel Monodentate Ferrocenyl Ligands For Enantioselective Au(I)-Catalyzed 1,6-Enyne Cyclizations

Identifier:  TDX:4559

Handle: https://hdl.handle.net/20.500.11797/TDX4559

Authors:  Mora Forte, Pablo

Abstract:
The development of new chiral ligands is key for the advancement of asymmetric transition-metal catalysis. In the last two decades, the field of homogeneous gold(I) catalysis has seen great progress owing to the ability of gold(I) catalysts to activate alkynes with high selectivity under very mild conditions.The slow progress in asymmetric gold(I)- catalyzed reactions stems from the difficulty of positioning the ligand chiral information close to the reactive center, especially in activating non-prochiral alkynes. As a consequence, novel ligands adequated to the intricacies of gold(I) catalysis are needed to develop enantioselective transformations. The first chapter describes the design and development of novel chiral ligands based on ferrocenyl phosphines for enantioselective gold(I) catalysis.The new chiral gold(I) complexes were applied in the enantioselective gold(I) catalyzed [4+2] cycloaddition and alkoxycyclization of 1,6-enynes with good to excellent enantioselectivity.The second chapter focuses on understanding the mode of enantioinduction by a combination of experimental and computational studies. Additionally, a predictive model for enantioselectivity was generated based on the results obtained.