Synthesis of 5,6,11,12-tetrahydrodibenzo[b,f][1,5]diazocines and a demonstration of their reactivity to afford methano strap-modified Tröger’s base analogues

Abstract

Tröger's base analogues are of interest in areas such as host-guest chemistry, synthetic receptor design and asymmetric catalysis. We foresee that access to diverse functionality attached to the bridge of Tröger's base compounds will be beneficial for the development of these applications. As a starting point, we report a facile and general methodology to prepare a range of diversely functionalised 5,6,11,12-tetrahydrodibenzo[b,f][1,5]diazocines, compounds that may be viewed as "strap-clipped" Tröger's bases. As a demonstration of their reactivity, these compounds were reacted with benzaldehyde to introduce phenyl substituted straps onto a Tröger's base framework.

Experimental, Spectroscopic, and Computational Insights into the Reactivity of “Methanal” with 2-Naphthylamines

“…Since neither bisnapthylamine 18a nor acridine 5a were present in the crude product, and dinaphthylamine 17a was isolated in a very low yield, a rearrangement of 17a into 18a during the chromatography could be considered, followed by the conversion of 18a into acridine 5a , since 18a was the expected intermediate product of 5a [ 1 , 23 ]. A similar rearrangement and formation of 18b when exposed to silica or to air and ambient light for prolonged periods have previously been described [ 24 ].…”

Facile Preparation of Λ-Shaped Building Blocks: Hünlich Base Derivatization

“…Hünlich's base was subjected to the method described in the literature. 3 The amount of obtained product was not sufficient to be properly characterized, despite scaling up the reaction tenfold. [1,5] diazocine-1,7diamine (0.60 g, 2.0 mmol, 1.0 eq.)…”

Tröger’s Base Chemistry in Solution and in Zr(IV)-Based Metal–Organic Frameworks

“…Typically, TB analogs are synthesized through acid-catalyzed condensation reactions of substituted aniline derivatives with formaldehyde or one of its precursors, which enables straightforward functionalization of the aryl rings. To introduce functionalities onto the methylene strap of a TB analogue, a synthetic method of directly inserting the functionalized methylene strap into the cyclic secondary diamine precursor was developed, where TB derivatives were first transformed into their strap-clipped forms. − Despite its noteworthy structure and functionality, strap-clipped TB chemistry has been largely overlooked and is completely unknown in metal–organic framework (MOF) solids.…”