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Diversification of the structures and the applications possible for foldamers rely on expansion of the building block library available for their synthesis. In this work, we describe the synthesis of a range of three dimensional heteroaromatic monomers, based on iptycene scaffolds, that are suitable for the synthesis of aromatic oligoamide foldamers. These units can be obtained in gram quantities in up to 80 % yield through [4+2] cycloaddition between diester, diamine, and amino acid derivatives of 1,8‐diazaanthracenes and a variety of dienophiles. X‐ray structural studies of the monomers and an oligomer show that the new motif orients the two heterocyclic rings and attached groups at an angle of approximately 120° to each other, opening new geometric considerations for the design of this class of foldamer. [ABSTRACT FROM AUTHOR]

The postsynthetic modulation of capsules based on helical aromatic oligoamide foldamers would be a powerful approach for controlling their receptor properties without altering the initial monomer sequences. With the goal of developing a method to increase the size of a cavity within a helix, a single-helical foldamer capsule was synthesized with a wide-diameter central segment that was designed to intercalate with a second shorter helical strand. Despite the formation of stable double-helical homodimers ( Kdim>107 M−1) by the shorter strand, when it was mixed with the single-helical capsule sequence, a cross-hybridized double helix was formed with Ka>105 M−1. This strategy makes it possible to direct the formation of double-helical heterodimers. On the basis of solution- and solid-state structural data, this intercalation resulted in an increase in the central-cavity size to give a new interior volume of approximately 150 Å3. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]