Division of Applied Chemistry, Graduate School of Natural Science and Technology, and Research Institute for Interdisciplinary Science, Okayama University, 3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530, Japan.
Chem Commun (Camb). 2019 Feb 19;55(16):2332-2335. doi: 10.1039/c9cc00270g.
Combined use of oxorhenium catalysts with triphenyl phosphite as an oxygen acceptor allowed efficient deoxygenative aromatization of oxabicyclic dienes. The reaction proceeded under neutral conditions and was compatible with various functional groups. Combining this deoxygenation with regioselective bromination and trapping of the generated aryne with furan resulted in benzannulative π-extension at the periphery of the PAHs. This enabled direct use of unfunctionalized PAHs for extension of π-conjugation. Iteration of the transformations increased the number of fused-benzene rings one at a time, which has the potential to alter the properties of PAHs by fine-tuning the degree of π-conjugation, shape, and edge topology.
将铼-氧催化剂与三苯基膦结合使用作为氧受体，可实现氧杂双环二烯的高效脱氧芳构化。该反应在中性条件下进行，并且与各种官能团相容。将脱氧反应与区域选择性溴化结合，并将生成的芳炔与呋喃捕获，可在 PAHs 的外围实现苯并环化的π-扩展。这使得可以直接使用未官能化的 PAHs 来扩展π共轭。通过重复这些转化，每次增加一个稠合苯环的数量，这有可能通过精细调节π共轭、形状和边缘拓扑结构来改变 PAHs 的性质。
