Jagtap Rahul A, Nishioka Yuki, Geddis Stephen M, Irie Yu, Takanashi Tsukasa, Adachi Rintaro, Yamakata Akira, Fuki Masaaki, Kobori Yasuhiro, Mitsunuma Harunobu, Kanai Motomu
Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
Graduate School of Natural Science & Technology, Okayama University, Okayama, 700-8530, Japan.
Nat Commun. 2025 Jan 9;16(1):428. doi: 10.1038/s41467-024-55460-y.
The advancement of an effective hydrogen liberation technology from liquid organic hydrogen carriers, particularly cycloalkanes such as cyclohexane and methylcyclohexane, holds significance in realizing a hydrogen-centric society. However, the attainment of homogeneous catalytic acceptorless dehydrogenation characterized by elevated selectivity for thorough aromatization under mild conditions remains unrealized. In this study, a catalyst system, facilitated by a double hydrogen atom transfer processes, has been devised for the catalytic acceptorless dehydrogenation of inert cycloalkanes at ambient temperature under visible light irradiation. Through the synergistic utilization of tetrabutylammonium chloride and thiophosphoric acid hydrogen atom transfer catalysts, successful catalytic acceptorless dehydrogenation with comprehensive aromatization has been accomplished with potential liquid organic hydrogen carrier candidates and showcased high functional group tolerance.
从液态有机氢载体，特别是环己烷和甲基环己烷等环烷烃中开发有效的氢释放技术，对实现以氢为中心的社会具有重要意义。然而，在温和条件下实现具有高选择性彻底芳构化的均相催化无受体脱氢仍未实现。在本研究中，设计了一种由双氢原子转移过程促进的催化剂体系，用于在可见光照射下室温下对惰性环烷烃进行催化无受体脱氢。通过协同使用四丁基氯化铵和硫代磷酸氢原子转移催化剂，已成功地对潜在的液态有机氢载体候选物进行了具有全面芳构化的催化无受体脱氢，并展示了高官能团耐受性。
