1583244-77-2Relevant academic research and scientific papers
Gold-catalyzed cyclization of diynes: Controlling the mode of 5-endo versus 6-endo cyclization - An experimental and theoretical study by utilizing diethynylthiophenes
Hansmann, Max M.,Tsupova, Svetlana,Rudolph, Matthias,Rominger, Frank,Hashmi, A. Stephen K.
supporting information, p. 2215 - 2223 (2014/03/21)
Herein, a dual-gold catalyzed cyclization of 3,4-diethynylthiophenes generating pentaleno[c]thiophenes through gold-vinylidenes and C-H bond activation is disclosed. Various new heteroaromatic compounds - substrate classes unexplored to date - exhibiting 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of the cyclization mode in the bifurcated cyclization area demonstrated that classical transition-state theory is no longer valid to explain the high experimentally observed selectivity.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. Copyright
