Synthesis and Retrostructural Analysis of Libraries of AB₃ and Constitutional Isomeric AB₂ Phenylpropyl Ether-Based Supramolecular Dendrimers

Abstract

We report the synthesis of methyl esters of 3-(4-hydroxyphenyl)propionic, 3-(3,4-dihydroxyphenyl)propionic, 3-(3,5-dihydroxyphenyl)propionic, and 3-(3,4,5-trihydroxyphenyl)propionic acids and their use in a convergent iterative strategy to prepare up to four generations of three libraries, one of 3,4,5- and two of constitutional isomeric 3,4- and 3,5-substituted 3-phenylpropyl dendrons. Each library contains 3-[3,4,5-tris(dodecyl-1-oxy)phenyl]propyl-, 3-[3,4-bis(dodecyl-1-oxy)phenyl]propyl-, 3-{3,4-bis[3-(4-dodecyl-1-oxyphenyl)propyl-1-oxy]phenyl}propyl-, and 3-{3,4,5-tris[3-(4-dodecyl-1-oxyphenyl)propyl-1-oxy]phenyl}propyl ether first-generation dendrons on their periphery and -CO2CH3, -COOH, and -CH2OH groups at their apex. Regardless of their generation number and their periphery, internal, and apex structures, these dendrons self-assemble into supramolecular dendrimers that self-organize into all periodic and quasi-periodic assemblies encountered previously and in several unencountered with architecturally related benzyl ether-based supramolecular dendrimers. A variety of porous columnar lattices that were previously obtained only from dendritic dipeptides and hollow supramolecular spheres were also discovered from these building blocks. The more flexible and less compact 3-phenylpropyl ether repeat units are stable under acidic conditions, facilitate a simpler synthetic strategy, provide faster dynamics of self-assembly into higher-order supramolecular structures of larger dimensions, exhibit lower transition temperatures than the corresponding benzyl ether homologues, and demonstrate the generality of the self-assembly concept based on amphiphilic dendrons.

Controlling the growth and shape of chiral supramolecular polymers in water

“…6), which confirms the results from SAXS and diffusion ordered spectroscopy (DOSY) measurements. According to these findings, we have been able to obtain self-assembled discrete objects that can be considered the supramolecular equivalent of dendritic macromolecules (49,50).…”

Síntese de β-D-galactopiranosídeos de arila diméricos para avaliação de sua interação com a lectina de Erythrina cristagalli

“…No planejamento de 6 e 7 levou-se em consideração que a LEC tem maior afinidade por galactosídeos aromáticos de configuração beta. 24 A cadeia lateral com três átomos de carbono, introduzida utilizandose a modificação de Doebner da reação de Knoavenagel, 25 além de servir como espaçador, permite a variação estrutural pela redução da ligação dupla, gerando derivados com tendências conformacionais diferentes. Ademais, o produto obtido na reação de Doebner apresenta um grupo carboxila terminal, que pode ser convertido em outros grupos funcionais de interesse.…”

Self-interrupted synthesis of sterically hindered aliphatic polyamide dendrimers

“…Their nanoarchitecture emerges by increasing their generation number from ellipsoidal or disk-like 2D to 3D globular constructs (16,(19)(20)(21)(22)(23)(24)(25). Their core and branch multiplicities, as well as branch cell segment length (l), determine the generation number at which dendrimers become globular (19)(20)(21).…”

“…Dendrimers synthesized by divergent iterative methods are expected to contain their functional groups, which increase in number with core and branch multiplicities as well as with their generation number, at the periphery of their 2D or 3D architectures (16,19,21). Dendrons and dendrimers produced by convergent strategies contain one functional group at their apex, whereas the rest of them are at their periphery (16,17,20,(23)(24)(25). Ultimately at a certain generation, dendrons also become globular dendrimers with their functional group from the apex becoming encapsulated at the core of the globular object (22)(23)(24)(25).…”

“…Dendrons and dendrimers produced by convergent strategies contain one functional group at their apex, whereas the rest of them are at their periphery (16,17,20,(23)(24)(25). Ultimately at a certain generation, dendrons also become globular dendrimers with their functional group from the apex becoming encapsulated at the core of the globular object (22)(23)(24)(25). The large concentration of functional groups at the periphery of the globular object inspired a diversity of functions of biomedical interest that are not accessible with their linear homologs (26)(27)(28)(29)(30)(31).…”