Gold-Catalyzed Cyclization of Diynes: Controlling the Mode of 5-endo versus 6-endo Cyclization-An Experimental and Theoretical Study by Utilizing Diethynylthiophenes

Herein, a dual-gold catalyzed cyclization of 3,4-diethynylthiophenes generating pentaleno[c]thiophenes through gold-vinylidenes and CH bond activation is disclosed. Various new heteroaromatic compoundssubstrate classes unexplored to dateexhibiting three five-membered annulated ring systems could be synthesized in moderate to high yields. By comparison of the solid-state structures of the corresponding gold-acetylides, it could be demonstrated that the cyclization mode (5-endo versus 6-endo) is controlled by the electronic and not steric nature of the diyne backbone. Depending on different backbones, we calculated thermodynamic stabilities and full potential-energy surfaces giving insight into the crucial dual-activation cyclization step. In the case of the 3,4-thiophene backbone, in which the initial cyclization is rate and selectivity determining, two energetically distinct transition states could be localized explaining the observed 5-endo cyclization mode by classical transition-state theory. In the case of vinyl and 2,3-thiophene backbones, the theoretical analysis of the cyclization mode in the bifurcated cyclization area demonstrated that classical transition-state theory is no longer valid to explain the high experimentally observed selectivity. Herein, for the first time, the influence of the backbone and the aromatic stabilization effect of the 6-endo product in the crucial cyclization step could be visualized and quantified by calculating and comparing the full potential-energy surfaces.