Macrocycles in catalysis: New applications and methodologies

Macrocycles are a versatile class of compounds with extensive applications across various fields of chemistry, particularly in sensor development, molecular machines, and catalysis. This work explores novel applications of macrocycles in transition metal-catalyzed reactions. The findings can be summarized as follows: Chapter 2 details the synthesis and characterization of three new dimeric calix[6]arene-based gold(I) complexes. The influence of the macrocyclic cavity on these complexes’ catalytic activity is investigated, specifically in the gold(I)-catalyzed cycloisomerization of 1,6-dienynes. In Chapter 3, the focus shifts to the use of gold(I)-catalyzed hydroarylation for synthesizing inherently chiral calix[4]arene derivatives. Preliminary studies toward developing enantioselective methodologies are also included. Chapter 4 describes a regioselective distal functionalization of the upper rim of calix[4]arene derivatives via iridium-catalyzed C-H borylation. The versatility of these valuable intermediates is also discussed. Finally, Chapter 5 presents a new synthetic approach for preparing indene-based natural products using an enantioselective gold(I)-catalyzed alkoxycycloisomerization reaction facilitated by resorcin[4]arene-based gold(I) complexes.