Synthesis of 1,8-Diazaanthracenes as Building Blocks for Internally Functionalized Aromatic Oligoamide Foldamers

Abstract

The synthesis of a variety of 9-functionalized 1,8-diazaanthracene diesters and amino acids is described. Derivatization at the 9-position relies on facile reactions performed on the 9-chloro and 9-bromomethyl precursors. This has allowed the incorporation of nucleophilic or sensitive functional groups that otherwise cannot be incorporated under standard methods for synthesizing these compounds. Additionally, the synthesis of the protected amino acids via a high-yielding monosaponification and subsequent Curtius rearrangement has been accomplished on a multigram scale. These units, together with the functionalized derivatives, should prove to be useful monomers in the synthesis of aromatic oligoamide foldamers.

Iterative design of a helically folded aromatic oligoamide sequence for the selective encapsulation of fructose

“…For other families of guests, or to achieve binding in polar or even protic media 32,45 , new building blocks may be required to bring hydrophobic moieties or charges into the capsule cavity. Efforts in this direction are currently being made in our laboratory 46 . Expanding our approach to other large and complex guest molecules would enable the fabrication of novel generations of selective receptors, sensors and transporters.…”

Fluorescent Short‐Stranded Helical Foldamers Based on L‐shaped Dibenzopyrrolo[1,2‐a][1,8]naphthyridine

“…Synthetic helical foldamers, [1][2][3][4][5][6][7][8][9][10] which fold into ah elical form from random coils spontaneously or in response to stimuli, have attracted attentionf or use as peptidem imetics, selective guest recognition, stimuli-responsive supramolecules, and chiral recognition.F or flexible foldamers,ahelical conformation is not alwaysf avored because ad ecrease in flexibility can lead to entropyloss. Thus, mostarene-based foldamers use enthalpicallyf avorable interactions, such as hydrogen bonds, [3][4][5] solvophobic effects, [2,6,9] and guest binding [7,10] in addition to p-p stacking to promote ah elical conformation from a random coil. In this context, curved and rigid arene units [5] would be promising candidates to constructe ntropically favorable helical foldamers with am inimal number of units and rotatable bonds per one turn compared with conventionalm ultiunit type helical foldamers.…”

Light‐Controlled Conformational Switch of an Aromatic Oligoamide Foldamer

“…[20,21] Thus,r elated 1,8-diazaanthracenes (i.e., pyrido-[3,2-g]quinolines) undergo quantitative antiparallel photodimerization in solution (Figure 1a;s ee Figure S1 in the Supporting Information). It comprises two 1,8-diazaanthracenes, [23] A H ,s eparated by ad initro-diamino-benzene turn, [24] T. Upon irradiation under anaerobic conditions at 320 < l < 390 nm using a5 0W lamp and appropriate cutoff filters, 1 HNMR monitoring showed the quantitative conversion of 1 into as ingle new product having the same mass in 20 minutes (see Figure S1). [18] This observation led us to consider the production of parallel photoproducts guided by folding ( Figure 1c).…”