N‐Alkylated Aromatic Poly‐ and Oligoamides

Abstract

N-alkylated aromatic poly-and oligoamides are a particular class of abiotic foldamers that is deprived of the capability of forming intramolecular hydrogen-bonding networks to stabilize their tri-dimensional structure. The alkylation of the backbone amide nitrogen atoms greatly increases the chemical diversity accessible for aromatic poly-and oligoamides. However, the nature and the conformational preferences of the N,N-disubstituted amides profoundly modify the folding properties of these aromatic poly-and oligoamides. In this Review, representative members of this class of aromatic poly-and oligoamides will be highlighted, among them N-alkylated phenylene terephthalamides, benzanilides, pyridylamides, and aminomethyl benzamide oligomers. The principal synthetic pathways to the main classes of N-alkylated aromatic polyamides with narrow to broad molecular-weight distribution, or oligoamides with specific sequences, will be detailed and their foldameric properties will be discussed. The Review will end by describing the few applications reported to date and future prospects for the field.

Conformational Control of ortho-Phenylenes by Terminal Amides

“…Third, there is the cis versus trans configuration of the amides. Changes in ϕ N are expected to be slow on the NMR time scale, − but the trans amide is expected to be substantially more stable than the cis. , Thus, ϕ N is not likely to contribute meaningfully populated alternate conformers because the trans form should predominate. This is confirmed by DFT studies of model systems described in the Supporting Information.…”

Conformational control of ortho-phenylenes by terminal amides

“…27 Third, there is the cis vs trans configuration of the amides. Changes in ϕ N are expected to be slow on the NMR time scale, [36][37][38] but the trans amide is expected to be substantially more stable than cis. 39,40 Thus ϕ N is not likely to contribute meaningfully populated alternate conformers since the trans form should predominate.…”

Arylopeptoid oligomers functionalised by combinatorial or sequential on-resin click chemistry using a copper(i)–N-heterocyclic carbene catalyst

“…N -Alkylated aromatic oligoamides are a class of oligomers that are still underexplored. 1 Contrary to other aromatic oligoamides relying on hydrogen-bonding networks for their structuration, 2 the conformational modularity and adaptability of N -substituted aromatic oligoamides make them particularly interesting abiotic oligomers for applications in the medical and/or materials field. 1 One major issue for their development is the ability to provide well-defined sequences with high chemical diversity.…”

“…1 Contrary to other aromatic oligoamides relying on hydrogen-bonding networks for their structuration, 2 the conformational modularity and adaptability of N -substituted aromatic oligoamides make them particularly interesting abiotic oligomers for applications in the medical and/or materials field. 1 One major issue for their development is the ability to provide well-defined sequences with high chemical diversity. Toward this aim, N -substituted aminomethylbenzamide oligomers are particularly well adapted and represent particularly promising aromatic oligoamides.…”