Synthesis of the First Resorcin[4]arene-Functionalized Triazolium Salts and Their Use in Suzuki–Miyaura Cross-Coupling Reactions

Abstract

Two bulky triazolium salts, namely 1-{4(24),6(10),12(16),18(22)-tetramethylenedioxy- 2,8,14,20-tetrapentylresorcin[4]arene-5-yl}-4-phenyl-3-methyl-1H-1,2,3-triazolium tetrafluoro borate (1) and 1,4-bis{4(24),6(10),12(16),18(22)-tetramethylenedioxy-2,8,14,20-tetrapentyl resorcin[4]arene-5-yl}-3-methyl-1H-1,2,3-triazolium iodide (2), have been synthesized and assessed in the palladium-catalyzed Suzuki−Miyaura cross-coupling of aryl chlorides, with aryl boronic acids. As a general trend, the reaction rates obtained with 1 were significantly higher (up to 5 times) than those observed for 2, this mainly reflected a sterically more accessible metal center in the catalytic intermediates formed with 1. The presence of flexible pentyl chains in these intermediates, which might sterically interact with the metal center, when the latter adopts an exo-orientation with respect to the cavity, were likely responsible for the observed good performance.

Keywords

• resorcinarene
• triazolium salt
• Suzuki–Miyaura cross-coupling