Bergman cyclization

Abstract: The Bergman cyclization is one of the most fascinating rearrangements in chemistry, with important implications in organic synthesis and pharmacology. Here we demonstrate a reversible Bergman cyclization for the first time. We induced the on-surface transformation of an individual aromatic diradical into a highly strained ten-membered diyne using atomic manipulation and verified the products by non-contact atomic force microscopy with atomic resolution. The diyne and diradical were stabilized by using an ultrathin NaCl film as the substrate, and the diyne could be transformed back into the diradical. Importantly, the diradical and the diyne exhibit different reactivity, electronic, magnetic and optical properties associated with the changes in the bond topology, and spin multiplicity. With this reversible, triggered Bergman cyclization we demonstrated switching on demand between the two reactive intermediates by means of selective C-C bond formation or cleavage, which opens up the field of radical chemistry for on-surface reactions by atomic manipulation.

Abstract: Seven criteria are developed and discussed that lead to the design of a new enediyne anticancer drug, which should have low toxicity but high biological selectivity and activity when attacking the DNA of tumor cells. These criteria concern (among others) the thermodynamic and kinetic stability of the species involved in the reaction of an enediyne, the biradical character and H-abstraction ability of the intermediate biradical generated in a Bergman reaction of the enediyne, and the basicity of the enediyne and its associated biradical. Thirteen different heteroenediynes were investigated with the help of B3LYP/6-31G(d,p) calculations to find a suitable candidate for a new enediyne anticancer drug, which fulfills the seven criteria. These calculations included the determination of reaction profiles for Bergman and retro-Bergman reactions, the calculation of singlet−triplet splittings of biradicals formed from enediynes, and the prediction of pKa values. Results were tested by using a larger basis set (6-3...

Abstract: Reaction coordinates are computed for the Bergman cyclizations of hex-3-en-1,5-diyne and neutral and protonated 3-azahex-3-en-1,5-diyne at various levels of correlated electronic structure theory, as are singlet−triplet splittings for intermediate arynes. To be effective in low-symmetry situations showing high degrees of biradical character, CCSD(T) calculations benefit from use of Brueckner orbitals. Replacement of a CH fragment by N is predicted to increase the stability of the aryne relative to the iminediyne, and to increase drastically the stability of the isomeric enynenitrile. The barrier for retro-aza-Bergman cyclization of 2,5-pyridyne to pent-3-en-1-ynenitrile is predicted to be only 0.9 kcal/mol, which, combined with a predicted singlet−triplet splitting of −11.6 kcal/mol, suggests that 2,5-pyridynes are poor hydrogen atom abstracting agents. Protonation of nitrogen decreases the singlet−triplet splitting and raises the barrier to retro-aza-Bergman cyclization such that protonated 2,5-pyridynes...

Abstract: On-surface fabrication of covalently interlinked conjugated nanostructures has attracted significant attention, mainly because of the high stability and efficient electron transport ability of these structures. Here, from the interplay of scanning tunneling microscopy imaging and density functional theory calculations, we report for the first time on-surface formation of one-dimensional polyphenylene chains through Bergman cyclization followed by radical polymerization on Cu(110). The formed surface nanostructures were further corroborated by the results for the ex situ-synthesized molecular product after Bergman cyclization. These findings are of particular interest and importance for the construction of molecular electronic nanodevices on surfaces.