Combining Two Methods of Sequence Definition in a Convergent Approach: Scalable Synthesis of Highly Defined and Multifunctionalized Macromolecules

Solleder, Susanne C.; Martens, Steven; Espeel, Pieter; Prez, Filip Du; Meier, Michael A. R.

doi:10.1002/chem.201703877

Cited by 29 publications

(18 citation statements)

References 29 publications

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“…[19][20][21] Various strategies have been proposed for regulating monomer sequence and chain length of synthetic polymers, including condensation chain polymerization, 22 alternating radical polymerization, [23][24][25][26][27][28][29] anionic polymerization, [30][31] ring-opening or cross metathesis polymerization, [32][33][34] atom transfer radical addition (ATRA), [24][25][35][36][37] iterative exponential growth, [38][39][40][41][42][43] single unit monomer insertion 12,[44][45][46][47][48][49][50] and various organic coupling, condensation or "click" addition reactions. 19,[51][52][53][54][55][56][57][58][59][60][61][62]…”

Section: Introductionmentioning

confidence: 99%

Discrete and Stereospecific Oligomers Prepared by Sequential and Alternating Single Unit Monomer Insertion

et al. 2018

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Natural biopolymers, such as DNA and proteins, have uniform microstructures with defined molecular weight, precise monomer sequence, and stereoregularity along the polymer main chain that affords them unique biological functions. To reproduce such structurally perfect polymers and understand the mechanism of specific functions through chemical approaches, researchers have proposed using synthetic polymers as an alternative due to their broad chemical diversity and relatively simple manipulation. Herein, we report a new methodology to prepare sequence-controlled and stereospecific oligomers using alternating radical chain growth and sequential photoinduced RAFT single unit monomer insertion (photo-RAFT SUMI). Two families of cyclic monomers, the indenes and the N-substituted maleimides, can be alternatively inserted into RAFT agents, one unit at a time, allowing the monomer sequence to be controlled through sequential and alternating monomer addition. Importantly, the stereochemistry of cyclic monomer insertion into the RAFT agents is found to be trans-selective along the main chains due to steric hindrance from the repeating monomer units. All investigated cyclic monomers provide such trans-selectivity, but analogous acyclic monomers give a mixed cis- and trans-insertion.

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Section: Introductionmentioning

confidence: 99%

Discrete and Stereospecific Oligomers Prepared by Sequential and Alternating Single Unit Monomer Insertion

et al. 2018

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“…This chemistry has been explored on the solid phase by immobilizing a functional thiolactone molecule on a solid resin in a Merrifield‐inspired synthesis route . This is advantageous as it allows us to work with a high excess of reagents (thus high concentration to improve kinetics and chance of 100% conversion) and to easily purify after each step by solvent washing, as compared to solution‐phase approaches, which require time‐consuming purifications …”

Section: Methodsmentioning

confidence: 99%

Automated Synthesis Protocol of Sequence‐Defined Oligo‐Urethane‐Amides Using Thiolactone Chemistry

Holloway

Mertens

Prez

et al. 2018

Macromol. Rapid Commun.

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An automated, iterative protocol for the synthesis of multifunctional, sequence‐defined oligo‐urethane‐amides using thiolactone chemistry is reported. Here, sequenced functionalization of the backbone is easily introduced using commercially available primary amines. The chemistry is carried out on solid phase using different supports for better optimization of the synthetic protocol and in order to demonstrate the versatility of the approach. This technique is very effective for iterative synthesis and solid‐phase chemistry and enables the exploration of full automation of this approach using a robotic peptide synthesizer. As a result, this automated protocol allows for the synthesis of a sequence‐defined nonamer of high purity.

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“…Meier et al further extended coupling-activation approach toward sequence-defined oligomer by iterative Passerini reaction and thiolactone chemistry. [112] Barner-Kowollik and coworkers combined iterative Passerini reaction and photochemically induced Diels-Alder (DA) reaction to produce precision alternating oligomers with molecular weight up to 3532.16 g mol −1 . [113] Then, Meier et al explored couplingdeprotection approach based on iterative Passerini reaction ( Figure 10B).…”

Section: Iterative Multicomponent Reaction For the Synthesis Of Sequementioning

confidence: 99%

Multicomponent Reactions and Multicomponent Cascade Reactions for the Synthesis of Sequence‐Controlled Polymers

Zhang

You

Hong

2018

Macromol. Rapid Commun.

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Control over the monomer sequence during polymerization has attracted great attention in polymer science, but it remains a serious challenge. Recently, multicomponent reactions have been playing a significant role in the synthesis of sequence-controlled polymers due to their inherent advantage of combining three or more starting materials in time-saving, one-pot operations to afford complex microstructures. In this feature article, the recent representative developments in the synthesis of sequence-controlled polymers by multicomponent reactions are highlighted to give insight on the design of novel sequence-controlled polymers with sufficient molecular diversity and complexity. The main part of this article is divided into three sections according to the different polymerization strategies using multicomponent reactions: direct multicomponent polymerization, multicomponent cascade polymerization, and iterative multicomponent reaction, respectively. It is anticipated that this feature article may provide some guidance for the fabrication of sequence-controlled polymers by multicomponent reactions.

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Combining Two Methods of Sequence Definition in a Convergent Approach: Scalable Synthesis of Highly Defined and Multifunctionalized Macromolecules

Cited by 29 publications

References 29 publications

Discrete and Stereospecific Oligomers Prepared by Sequential and Alternating Single Unit Monomer Insertion

Discrete and Stereospecific Oligomers Prepared by Sequential and Alternating Single Unit Monomer Insertion

Automated Synthesis Protocol of Sequence‐Defined Oligo‐Urethane‐Amides Using Thiolactone Chemistry

Multicomponent Reactions and Multicomponent Cascade Reactions for the Synthesis of Sequence‐Controlled Polymers

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