Reversible [4 + 2] cycloaddition reaction of 1,3,2,5-diazadiborinine with ethylene

• Main Authors: Wu, Di, Ganguly, Rakesh, Li, Yongxin, Hoo, Sin Ni, Hirao, Hajime, Kinjo, Rei
• Other Authors: School of Physical and Mathematical Sciences
• Format: Article
• Language: English
• Published: 2018
• Subjects: Cycloaddition; Reaction Pathways; DRNTU::Science::Chemistry
• Online Access: https://hdl.handle.net/10356/89933; http://hdl.handle.net/10220/46438
• Institution: Nanyang Technological University

Under ambient conditions, a [4 + 2] cycloaddition reaction of 1,3,2,5-diazadiborinine 1 with ethylene afforded a bicyclo[2.2.2] derivative 2, which was structurally characterized. The cyclization process was found to be reversible, and thus retro-[4 + 2] cycloaddition reproduced 1 quantitatively, concomitant with the release of ethylene. Compound 1 reacted regio-selectively and stereo-selectively with styrene derivatives and norbornene, respectively, and these processes were found to be reversible too. Computational studies determined the reaction pathways which were consistent with the regio-selectivity observed in the reaction of styrene, and the reaction was suggested to be essentially concerted but highly asynchronous.