Epoxydibenzo[b,f][1,5]diazocines: From a Hidden Structural Motif to an Efficient Solvent-Free Synthetic Protocol

Abstract

Epoxydiazocines belong to the rare class of small V-shaped molecules, closely related to Tröger’s base. Due to their intriguing, unique structure, they could serve as molecular building blocks for supramolecular chemistry. An extensive review on their synthesis is contained in this article. Moreover, our recent findings devoted to efficient and easily scalable synthesis of fluorinated epoxy[1,5][b,f]diazocines through solvent-free base-catalyzed condensation of ortho-aminophenones is provided. The unique V-shaped structure was confirmed by X-ray crystal structure analysis. Furthermore, the rigidity of the epoxy­diazocine skeleton allowed for racemate separation and the configuration of enantiomers was established by combining quantum chemical calculations and chiroptical methods.1 Introduction2 Synthetic Efforts Towards Epoxydibenzo[b,f][1,5]diazocines3 Synthetic Efforts Towards Fluorinated Epoxydibenzo[b,f][1,5]diazocines4 Conclusion

Synthetic strategies and diversification of dibenzo[1,5]diazocines

“…Synthetic protocols for the preparation of epoxydibenzo [1,5] diazocine are rarely reported. 77 In 2011, Wang et al 78 showed the analogue can be obtained from the reaction of 2-amino-6bromo-4-(trifluoromethyl)benzaldehyde, phenyl ketone, 57a and sodium hydroxide in refluxing ethanol. Product 58 was synthesised in 40% yield with accompanying formation of substituted quinoline, 59 in 15% yield.…”