Abstract
A series of structurally differentiated α-cationic phospholes containing cyclopropenium, imidazolium, and iminium substituents has been synthesized by reaction of chlorophosphole 1 with the corresponding stable carbenes. Evaluation of the donor properties of these compounds reveals that their strong π-acceptor character is heavily influenced by the nature of the cationic group. The coordination chemistry of these newly prepared ligands towards Au(I) centers is also described and their unique electronic properties exploited in catalysis. Interestingly, α-cationic phosphole containing catalysts were not only able to accelerate model cycloisomerization reactions, but also to efficiently discriminate between concurrent reaction pathways, avoiding the formation of undesired product mixtures.