Synthetic Doping of Acenaphthylene through BN/CC Isosterism and a Direct Comparison with BN-Acenaphthene

• Published in: Journal of organic chemistry 2022-10, Vol.87 (19), p.12986-12996
• Main Authors: Zhang, Yanli, Li, Wenlong, Jiang, Ruijun, Zhang, Lei, Li, Yuanhao, Xu, Xiaoyang, Liu, Xuguang
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.2c01534

Boron/nitrogen-doped acenaphthylenes, a new class of BN-doped cyclopenta-fused polycyclic aromatic hydrocarbons, were synthesized via indole-directed C–H borylation. The reference molecule BN-acenaphthene was also synthesized in a similar manner. Both BN-acenaphthylene and BN-acenaphthene were unequivocally characterized by single-crystal X-ray analysis. The aromaticities of each ring in BN-acenaphthylenes were quantified by experimental and theoretical methods. Moreover, doping the BN unit into acenaphthylene can increase the LUMO level and decrease the HOMO level, resulting in wider HOMO–LUMO energy gaps. Furthermore, regioselective bromination of BN-acenaphthylene (B-Mes) afforded monobrominated BN-acenaphthylene in good yield. Subsequently, cross-coupling of brominated BN-acenaphthylene gave a series of BN-acenaphthylene derivatives. In addition, the photophysical properties of these BN-acenaphthylene derivatives can be fine-tuned by the substituents on the BN-acenaphthylene scaffold.