Synthesis of a novel NHC and analysis of its selectivity in Ni-catalyzed rearrangements of cyclopropylen-ynes

CHED 478

Kelly M Wiggins, Department of Chemistry, Austin College, 900 N Grand Ave 61735, Sherman, TX 75090 and Janis Louie, louie@chem.utah.edu, Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, UT 84112-0850.
It has been shown that the use of different N-heterocyclic carbenes (NHCs) as ligands in Ni-catalyzed rearrangements of cyclopropylen-ynes yields three different carbocyclic products, one with a five-membered ring and the others with seven-membered rings. Previous research used the NHCs IPr and ItBu in such rearrangements and showed that the ItBu ligand always yields the five-membered ring product whereas the IPr ligand gave a mixture of the five-membered ring product and the two seven-membered ring products depending on the substituent present off the alkyne. To further study the Ni-catalyzed rearrangement of cyclopropylen-ynes, it was desired to have an NHC ligand that was half IPr and half ItBu. In an attempt to study its selectivity, we have synthesized the novel ligand by an alternative route and have started to analyze its use as a ligand in Ni-catalyzed rearrangements. Synthetic protocol, yields and findings about the ligands selectivity will be presented.