Department of Pharamaceutical Chemistry, Kyoto Pharmaceutical University.
Department of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba.
Chem Pharm Bull (Tokyo). 2022;70(9):605-615. doi: 10.1248/cpb.c22-00217.
The preparation, optical resolution, and structural investigations of a series of axially chiral biaryl dicarboxylic acids bearing oxygen, sulfur, and selenium atoms were carried out. The crystal structures of sulfur- and selenium-containing derivatives revealed that the carboxy groups of these compounds are located in a co-planar geometry with the fused aromatic rings including the chalcogen atoms. These conformational controls were found to be achieved by chalcogen-bonding interactions between chalcogen atoms in the aromatic rings and oxygen atoms in the carboxy groups. Even in the case of a binaphthofuran derivative, in which the formation of chalcogen-bonding interactions was expected to be negligible, the carboxy groups were also found to be located in a co-planar geometry toward its fused cyclic rings. Natural bond orbital (NBO) analyses of these dicarboxylic acids indicated the formation not only for the chalcogen-bonding interactions for S and Se derivatives, but also the tetrel-bonding interactions between the oxygen atoms in the carboxy groups and the carbon atoms in the fused cyclic rings for all biaryl dicarboxylic acids. These tetrel-bonding interactions were thought to contribute to conformational control in the binaphthofuran derivative. Physical and chiroptical properties such as the racemization barriers and circular dichroism (CD) spectra of these biaryl dicarboxylic acids were also revealed.
我们进行了一系列含有氧、硫和硒原子的轴手性联苯二羧酸的制备、光学拆分和结构研究。含硫和硒的衍生物的晶体结构表明，这些化合物的羧基与包括杂原子在内的稠合芳环处于共面几何形状。这种构象控制是通过芳环中的杂原子与羧基中的氧原子之间的硫键相互作用实现的。即使在预期硫键相互作用形成可以忽略不计的联苯呋喃衍生物的情况下，也发现羧基也朝着其稠合的环状结构处于共面几何形状。这些二羧酸的自然键轨道（NBO）分析表明，不仅对于 S 和 Se 衍生物形成了硫键相互作用，而且对于所有联苯二羧酸，羧基中的氧原子与稠合环状结构中的碳原子之间也形成了四键相互作用。这些四键相互作用被认为有助于联苯呋喃衍生物的构象控制。还揭示了这些联苯二羧酸的物理和手性光学性质，如外消旋化势垒和圆二色性（CD）光谱。
