Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, United States.
J Am Chem Soc. 2021 Oct 27;143(42):17724-17743. doi: 10.1021/jacs.1c08502. Epub 2021 Oct 12.
Five libraries of natural and synthetic phenolic acids containing five AB, ten constitutional isomeric AB, one AB, and one AB were previously synthesized and reported by our laboratory in 5 to 11 steps. They were employed to construct seven libraries of self-assembling dendrons, by divergent generational, deconstruction, and combined approaches, enabling the discovery of a diversity of supramolecular assemblies including Frank-Kasper phases, soft quasicrystals, and complex helical organizations, some undergoing deracemization in the crystal state. However, higher substitution patterns within a single dendron were not accessible. Here we report three libraries consisting of 30 symmetric and nonsymmetric constitutional isomeric phenolic acids with unprecedented sequenced patterns, including two AB, three AB, eight AB, five AB, six AB, three AB, two AB, and one AB synthesized by accelerated modular-orthogonal Ni-catalyzed borylation and cross-coupling. A single etherification step with 4-(-dodecyloxy)benzyl chloride transformed all these phenolic acids, of interest also for other applications, into self-assembling dendrons. Despite this synthetic simplicity, they led to a diversity of unprecedented self-organizing principles: lamellar structures of interest for biological membrane mimics, helical columnar assemblies from rigid-solid angle dendrons forming Tobacco Mosaic Virus-like assemblies, columnar organizations from adaptable-solid angle dendrons forming disordered micellar-like nonhelical columns, columns from supramolecular spheres, five body-centered cubic phases displaying supramolecular orientational memory, rarely encountered in previous libraries forming predominantly Frank-Kasper phases, and two Frank-Kasper phases. Lessons from these self-organizing principles, discovered within a single generation of self-assembling dendrons, may help elaborate design principles for complex helical and nonhelical organizations of synthetic and biological matter.
五个包含五个 AB、十个构象异构 AB、一个 AB 和一个 AB 的天然和合成酚酸库由我们实验室以前以 5 到 11 步合成并报道。它们被用于通过发散的生成性、解构和组合方法构建七个自组装树突库，从而发现了包括弗兰克-卡珀相、软准晶和复杂螺旋组织在内的多种超分子组装体，其中一些在晶体状态下发生消旋。然而，在单个树突内更高的取代模式是不可行的。在这里，我们报告了由 30 个具有前所未有的序列模式的对称和非对称构象异构酚酸组成的三个库，包括两个 AB、三个 AB、八个 AB、五个 AB、六个 AB、三个 AB、两个 AB 和一个 AB，它们通过加速模块化正交镍催化的硼酸化和交叉偶联合成。用 4-(-十二烷氧基)苯甲基氯进行单一醚化步骤，将所有这些酚酸转化为自组装树突，它们也对其他应用感兴趣。尽管合成简单，但它们导致了前所未有的自组织原则的多样性：层状结构，用于生物膜模拟；刚性固体角树突形成烟草花叶病毒样组装的螺旋柱状组装；可适应固体角树突形成无序胶束样非螺旋柱状的柱状组织；来自超分子球体的柱状物；显示超分子取向记忆的五个体心立方相，在以前的库中很少遇到，主要形成弗兰克-卡珀相；和两个弗兰克-卡珀相。这些自组织原则的教训，是在单个自组装树突一代中发现的，可能有助于阐述复杂螺旋和非螺旋组织的合成和生物物质的设计原则。
