An unprecedented adduct 10 between triphenylphosphine (TPP) and 3,3-dimethyl-1,2,5-thiadiazolidine 1,1-dioxide (8) is described, which can be regarded las a stable source of the [Ph(3)P](+) species, and was utilized to efficiently promote the coupling between alcohols and carboxylic or nitrogen acids in a Mitsunobu-like manner.