From Gold-Catalyzed Asymmetric or Photoredox-Assisted Cyclizations to Rhodium-Catalyzed C¿H Alkynylations

Identifier:  TDX:3538

Handle: https://hdl.handle.net/20.500.11797/TDX3538

Authors:  Mayans Peñarrubia, Joan Guillem

Abstract:
Transition-metal catalysis is key for the discovery of new efficient chemical transformation. Over the past 20 years, the field of homogeneous gold catalysis has witnessed an exponential growth owing to the unique carbophilicity of gold(I) catalyst. In this context, the cyclization of enynes is one of the most powerful reactions since it gives rise to complex polycyclic structures form relatively simple substrates and has been applied in the total synthesis of several natural products and organic materials. The first chapter of this Doctoral Thesis discloses the development of a new gold (I)-catalyzed asymmetric cyclizations of enynes and its use in the first total synthesis of carexanes I, P and O, secondary metabolites isolated from roots and leaves of the Mediterranean plant Carex distachya. The second chapter focuses in expanding the scope of the above-mentioned gold-catalyzed cyclization of enynes by combining this chemistry with the recently reported gold(I)/gold(III) arylative methodologies. Finally, the third chapter describes our contribution to the field of C–H activation concerning the selective ortho-alkynylation of nitro(hetero)arenes catalyzed by rhodium(III).