Lithium-Mediated Mechanochemical Cyclodehydrogenation
- Kanna FujishiroKanna FujishiroDepartment of Chemistry, Graduate School of Science, Nagoya University, Nagoya 464-8602, JapanMore by Kanna Fujishiro
- Yuta MorinakaYuta MorinakaTokyo Research Center, Organic Materials Research Laboratory, Tosoh Corporation, 2743-1 Hayakawa, Ayase, Kanagawa 252-1123, JapanMore by Yuta Morinaka
- Yohei OnoYohei OnoTokyo Research Center, Organic Materials Research Laboratory, Tosoh Corporation, 2743-1 Hayakawa, Ayase, Kanagawa 252-1123, JapanMore by Yohei Ono
- Tsuyoshi TanakaTsuyoshi TanakaTosoh Corporation, 3-8-2 Shiba, Minato-ku, Tokyo 105-8623, JapanMore by Tsuyoshi Tanaka
- Lawrence T. Scott
- Hideto Ito*
- , and
- Kenichiro Itami*
Cyclodehydrogenation is an essential synthetic method for the preparation of polycyclic aromatic hydrocarbons, polycyclic heteroaromatic compounds, and nanographenes. Among the many examples, anionic cyclodehydrogenation using potassium(0) has attracted synthetic chemists because of its irreplaceable reactivity and utility in obtaining rylene structures from binaphthyl derivatives. However, existing methods are difficult to use in terms of practicality, pyrophoricity, and lack of scalability and applicability. Herein, we report the development of a lithium(0)-mediated mechanochemical anionic cyclodehydrogenation reaction for the first time. This reaction could be easily performed using a conventional and easy-to-handle lithium(0) wire at room temperature, even under air, and the reaction of 1,1′-binaphthyl is complete within 30 min to afford perylene in 94% yield. Using this novel and user-friendly protocol, we investigated substrate scope, reaction mechanism, and gram-scale synthesis. As a result, remarkable applicability and practicality over previous methods, as well as limitations, were comprehensively studied by computational studies and nuclear magnetic resonance analysis. Furthermore, we demonstrated two-, three-, and five-fold cyclodehydrogenations for the synthesis of novel nanographenes. In particular, quinterrylene (rylene or pentarylene), the longest nonsubstituted molecular rylene, was synthesized for the first time.
This article is cited by 1 publications.
- Nusret Celik, Berk Sezen, Furkan Sahin, Ahmet Ceylan, Mahmut Ruzi, Mustafa Serdar Onses. Mechanochemical Coupling of Alkylsilanes to Nanoparticles for Solvent-Free and Rapid Fabrication of Superhydrophobic Materials. ACS Applied Nano Materials 2023, 6 (16) , 14921-14930. https://doi.org/10.1021/acsanm.3c02489