Sequence-Defined Dithiocarbamate Oligomers via a Scalable, Support-free, Iterative Strategy

Abstract

Precise control over the monomeric sequence on natural sequence-defined polymers (SDPs) leads to their structural diversity and functions. However, absolute control over the monomeric sequence on a synthetic polymer remains a challenging process. Herein, we describe a supportfree, protection−deprotection-free, cost-effective, and fast iterative strategy for multigram production of a new class of SDP with a unique functional group, dithiocarbamate, a potential group for material and biomedical applications. The strategy is based on a unique monomer, named as amine-hydroxyl monomer, and a three-component reaction between the monomer, CS 2 , and terminal chloro group of the growing chain. The fast strategy allows us to synthesize a 5mer sequence-defined oligomer in 6 h. For a proof of concept, a range of aliphatic and aromatic groups have been incorporated at different sequences in the sequence-defined oligomer. This SDP platform has further been advanced by two ways: (i) multiple approaches for postsynthetic modification of SDP and (ii) increasing the chain length in a single step.

Aza-Oxa-Triazole Based Macrocycles with Tunable Properties: Design, Synthesis, and Bioactivity

“…The formed product (1, Scheme 1 ) proceeded to the next step after solvent extraction. The amine-hydroxyl derivative with the pendant amide functional group was synthesized by a two-step reaction as per the reported procedure [ 34 ]. The first step was the alkyl amine reaction with chloroacetyl chloride (d, Scheme 1 ) in the presence of triethylamine (TEA) as the base and dichloromethane (DCM) as the solvent to obtain e, Scheme 1 .…”

Backbone and side chain-linker tunability among dithiocarbamate, ester and amide in sequence-defined oligomers: synthesis and structure–property–function relationship

“…SDO3 was synthesized using our earlier reported strategy. 6 As the main focus of this study was to investigate the effect of these three key functional groups (DTC, ester and amide) on the properties and applications of the SDO, the pendant group or side-chain of the SDO was kept constant. The structures of the synthesised SDOs, their HPLC traces and their characterization by mass spectrometry are shown in Fig.…”

“…Taking inspiration from natural sequence-defined polymers (SDPs), like nucleic acids and peptides, materials are being designed by the sequential addition of specific monomers at preordained positions. This results in synthetic SDPs [1][2][3][4][5][6][7][8][9] with pendant group functionality, desirable chain length and defined monomeric sequence. However, all of the reports on the synthesis of SDPs focus on the same backbone with different hanging residues for a specific SDP class.…”

Hierarchical Nanomaterials Assembled from Peptoids and Other Sequence-Defined Synthetic Polymers

“…The development of scalable and efficient synthetic methods for sequence-defined polymers is crucial to the large-scale assembly and applications of the resulting assembled nanomaterials to fulfill the high demand of functional materials in the future. Besides the well-developed solution-phase and solid-supported ISG and IEG synthetic methods, the solid-phase submonomer synthesis can also be competitive. , In addition, the very recently reported scalable approaches that applying polar-inverse strategy, flow chemistry, , and protecting-group-free strategy facilitate the synthesis progress and enlarge the family of large-scale accessible sequence-defined synthetic polymers. In summary, given the rapid progress made in the development of new methods of synthesizing sequence-defined synthetic polymers, and techniques for characterization and understanding their self-assembly behaviors, we are confident that a bright and fascinating future is waiting for the molecular self-assembly of sequence-defined synthetic polymers into high-information content hierarchical materials that rival those found in biology.…”