Terminal Alkyne Coupling Reactions Through a Ring: Effect of Ring Size on Rate and Regioselectivity

Terminal alkyne coupling reactions promoted by rhodium(I) complexes of macrocyclic NHC‐based pincer ligands—which feature dodecamethylene, tetradecamethylene or hexadecamethylene wingtip linkers viz. [Rh(CNC‐n)(C2H4)][BArF4] (n=12, 14, 16; ArF=3,5‐(CF3)2C6H3)—have been investigated, using the bulky alkynes HC≡CtBu and HC≡CAr’ (Ar’=3,5‐tBu2C6H3) as substrates. These stoichiometric reactions proceed with formation of rhodium(III) alkynyl alkenyl derivatives and produce rhodium(I) complexes of conjugated 1,3‐enynes by C−C bond reductive elimination through the annulus of the ancillary ligand. The intermediates are formed with orthogonal regioselectivity, with E‐alkenyl complexes derived from HC≡CtBu and gem‐alkenyl complexes derived from HC≡CAr’, and the reductive elimination step is appreciably affected by the ring size of the macrocycle. For the homocoupling of HC≡CtBu, E‐tBuC≡CCH=CHtBu is produced via direct reductive elimination from the corresponding rhodium(III) alkynyl E‐alkenyl derivatives with increasing efficacy as the ring is expanded. In contrast, direct reductive elimination of Ar'C≡CC(=CH2)Ar’ is encumbered relative to head‐to‐head coupling of HC≡CAr’ and it is only with the largest macrocyclic ligand studied that the two processes are competitive. These results showcase how macrocyclic ligands can be used to interrogate the mechanism and tune the outcome of terminal alkyne coupling reactions, and are discussed with reference to catalytic reactions mediated by the acyclic homologue [Rh(CNC‐Me)(C2H4)][BArF4] and solvent effects. Reactions of rhodium(I) complexes of macrocyclic NHC‐based pincer ligands with terminal alkynes produce interpenetrated enyne derivatives and showcase how macrocyclic ligands can be used to interrogate the mechanism of and tune the outcome of terminal alkyne coupling reactions.