Facile Access to Organostibines via Selective Organic Superbase Catalyzed Antimony‐Carbon Protonolysis

Abstract

AbstractThe selective formation of antimony‐carbon bonds via organic superbase catalysis under metal‐ and salt‐free conditions is reported. This novel approach utilizes electron‐deficient stibine, Sb(C6F5)3, to give upon base‐catalyzed reactions with weakly acidic aromatic and heteroaromatic hydrocarbons access to a range of new aromatic and heteroaromatic stibines, respectively, with loss of C6HF5. Also, the significantly less electron‐deficient stibines, Ph2SbC6F5 and PhSb(C6F5)2 smoothly underwent base‐catalyzed exchange reactions with a range of terminal alkynes to generate the stibines of formulae PhSb(C≡CPh)2, and Ph2SbC≡CR [R=C6H5, C6H4‐NO2, COOEt, CH2Cl, CH2NEt2, CH2OSiMe3, Sb(C6H5)2], respectively. These formal substitution reactions proceed with high selectivity as only the C6F5 groups serve as a leaving group to be liberated as C6HF5 upon formal proton transfer from the alkyne. Kinetic studies of the base‐catalyzed reaction of Ph2SbC6F5 with phenyl acetylene to form Ph2SbC≡CPh and C6HF5 suggested the empirical rate law to exhibit a first‐order dependence with respect to the base catalyst, alkyne and stibine. DFT calculations support a pathway proceeding via a concerted σ‐bond metathesis transition state, where the base catalyst activates the Sb‐C6F5 bond sequence through secondary bond interactions.