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

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.

本研究报道了多种9位官能化1,8-二氮杂蒽二酯（1,8-diazaanthracene diesters）与氨基酸的合成路线。该类化合物的9位衍生化过程以9-氯代和9-溴甲基前驱体为原料，借助简便易行的反应得以实现。该策略可引入亲核性或对反应条件敏感的官能团，而这类官能团无法通过该类化合物的标准合成路径实现引入。此外，本研究通过高产率单皂化反应与后续柯蒂斯重排（Curtius rearrangement），实现了保护型氨基酸的多克级规模合成。上述结构单元与所制备的官能化衍生物，均可作为实用单体应用于芳香寡酰胺折叠体（aromatic oligoamide foldamers）的合成中。