Chemoselective Cleavage and Transamidation of Tertiary p-Methoxybenzyl Amides under Metal-Free Photoredox Catalysis DOI

Hee-Chan Jeong,

Hyo‐Jun Lee, Keiji Maruoka

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 21, 2024

A metal-free and mild cleavage of tertiary

Language: Английский

β-Triketones as Reactive Handles for Polymer Diversification via Dynamic Catalyst-Free Diketoenamine Click Chemistry DOI
Lucca Trachsel, Kevin A. Stewart, Debabrata Konar

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 16257 - 16267

Published: June 4, 2024

The spontaneous condensation of amines with β-triketones (TK), forming β,β′-diketoenamines (DKE) and releasing water as the sole byproduct, exhibits many hallmarks "click" reactions. Such characteristics render TKs a highly advantageous platform for efficient polymer diversification, even in biological contexts. Leveraging reversible addition–fragmentation chain transfer (RAFT) photoiniferter polymerization novel TK-containing vinylic monomers, we synthesized polymers containing pendent excellent control molecular weights, excess 106 g mol–1. Under mild, catalyst-free conditions, poly(β-triketone methacrylate) could be modified diverse scope plethora functional groups. high efficiency this functionalization approach was further emphasized when grafting-to poly(ethylene glycol)-amine resulting bottlebrushes weights reaching 2.0 × 107 Critically, while formed DKE linkages are stable under ambient they undergo catalyst-free, dynamic transamination at elevated temperatures, paving way associative covalent adaptable networks. Overall, introduce triketone moieties into methacrylate acrylamide polymers, establishing postpolymerization modification technique that facilitates ligation permissible conditions.

Language: Английский

Citations

13

Photoiniferter Polymerization: Illuminating the History, Ascendency, and Renaissance DOI
Rhys W. Hughes, Megan E. Lott,

Rebecca A. Olson S

et al.

Progress in Polymer Science, Journal Year: 2024, Volume and Issue: 156, P. 101871 - 101871

Published: Aug. 22, 2024

Language: Английский

Citations

13

Mechanochemically Promoted Functionalization of Postconsumer Poly(Methyl Methacrylate) and Poly(α‐Methylstyrene) for Bulk Depolymerization DOI
James B. Young, Sofia L. Goodrich,

James A. Lovely

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: July 15, 2024

We describe a methodology of post-polymerization functionalization to enable subsequent bulk depolymerization monomer by utilizing mechanochemical macro-radical generation. By harnessing ultrasonic chain-scission in the presence N-hydroxyphthalimide methacrylate (PhthMA), we successfully chain-end functionalize polymers promote bulk, achieving up 82 % poly(methyl methacrylate) (PMMA) and poly(α-methylstyrene) (PAMS) within 30 min. This method yields high-purity that can be repolymerized. Moreover, as compared most common methods depolymerization, this work is efficient with ultra-high molecular weight (UHMW) polymers, establishing potential address highly persistent, non-degradable all-carbon backbone plastic materials. Lastly, demonstrate expansion commercial cell cast PMMA, high degrees from post-consumer waste. first demonstration applying PhthMA-promoted strategies homopolymer PMMA PAMS prepared conventional polymerization methods.

Language: Английский

Citations

10

Photocontrolled radical polymerization for the synthesis of ultrahigh-molecular-weight polymers DOI
Shilong Zhu, Weina Kong,

Shuangqi Lian

et al.

Nature Synthesis, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

Language: Английский

Citations

1

Ultra-high molecular weight polymer synthesis via aqueous dispersion polymerization DOI Creative Commons
Cabell B. Eades, Kaden C. Stevens, David Cabrera

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Polymerization-induced self-assembly (PISA) is leveraged for the synthesis of ultra-high molecular weight polymers in concentrated but free-flowing dispersions.

Language: Английский

Citations

1

RAFT with Light: A User Guide to Using Thiocarbonylthio Compounds in Photopolymerizations DOI Creative Commons
Magdalena A. Bereś, Cyrille Boyer, Matthias Hartlieb

et al.

ACS Polymers Au, Journal Year: 2025, Volume and Issue: unknown

Published: March 27, 2025

Language: Английский

Citations

1

Electrochemical Postpolymerization Modification and Deconstruction of Macromolecules DOI
J. Márquez, Sean R. Gitter,

Graham C. Gilchrist

et al.

ACS Macro Letters, Journal Year: 2024, Volume and Issue: unknown, P. 1345 - 1354

Published: Sept. 25, 2024

Electrolysis is an emerging approach to polymer postpolymerization modification, deconstruction, and depolymerization. Electrochemical reactions are particularly appealing for macromolecular transformations because of their high selectivity, ability be externally monitored, intrinsic scalability. Despite these desirable features the recent resurgent use small-molecule electrochemical reactions, development electrolysis has been limited. Herein, we highlight examples driven by heterogeneous redox chemistry. Throughout our exploration electrolysis, provide perspective on opportunities continued investigation in this nascent field. Specifically, how targeted reaction through deeper mechanistic insight will expand scope materials that can (de)constructed with methods. As developed, expect emerge as a high-functioning complementary tool functionalization deconstruction.

Language: Английский

Citations

4

Regioselective Synthesis of β,γ-Unsaturated Amides from Unactivated Alkenes DOI Creative Commons

Sabela Vega-Ces,

Bogdan R. Brutiu, Daniel Kaiser

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 8, 2025

β,γ-Unsaturated amides are valuable substrates for downstream functionalization reactions but can be challenging to prepare. Herein, we introduce an approach featuring the regioselective addition of carbamoyl chlorides unactivated alkenes, present its scope and limitations, exemplify synthetic utility.

Language: Английский

Citations

0

A Versatile Flow Reactor Platform for Machine Learning Guided RAFT Synthesis, Amidation of Poly(Pentafluorophenyl Acrylate) DOI Creative Commons
Alexander P. Grimm, Stephen T. Knox, Clarissa Y. P. Wilding

et al.

Macromolecular Rapid Communications, Journal Year: 2025, Volume and Issue: unknown

Published: April 8, 2025

Abstract Data‐driven polymer research has experienced a dramatic upswing in recent years owing to the emergence of artificial intelligence (AI) alongside automated laboratory synthesis. However, chemical complexity polymers employed synthesis still lacks terms defined functionality meet need next‐generation high‐performance materials. In this work, self‐optimization reversible addition‐fragmentation chain‐transfer (RAFT) polymerization pentafluorophenyl acrylate (PFPA) is presented, versatile building‐block enabling efficient post‐polymerization modifications (PPM). The system consisted computer‐operated flow reactor with orthogonal analytics comprising an inline benchtop nuclear magnetic resonance (NMR) spectrometer, and online size exclusion chromatography (SEC). This setup enabled automatic determination optimal conditions by implementation multi‐objective Bayesian algorithm. obtained poly(PFPA) precisely modified amidation taking advantage active (PFP) ester. By controlling feed ratios solutions containing different amines, their incorporation ratio into polymer, therefore its resulting properties, can be tuned predicted, which shown using NMR, differential scanning calorimetry (DSC), infrared (IR) analysis. described strategy represents method synthesize modify reactive continuous flow, expanding range functional materials accessible continuous, high‐throughput

Language: Английский

Citations

0

Oxidative Polymer Degradation via Cope Elimination DOI
Jared I. Bowman, James B. Young,

Victoria L. Thompson

et al.

Macromolecules, Journal Year: 2024, Volume and Issue: 57(15), P. 7547 - 7555

Published: July 31, 2024

We report on a mild and efficient method to degrade poly(β-amino esters) (PBAEs) poly(amido amines) (PAMAMs) via Cope elimination. Oxidation of backbone tertiary amines N-oxides allowed for the spontaneous abstraction acidic β ester/amide protons, resulting in subsequent chain cleavage. show that quantitative PBAE degradation can be achieved within 15 min several organic solvents by treatment with meta-chloroperbenzoic acid. Despite being more robust substrate than PBAEs, PAMAMs could also fully degraded 18 h an aqueous protocol hydrogen peroxide. Mass spectrometry revealed similar profiles PBAEs vinyl, divinyl, dihydroxylamine compounds major byproducts. Finally, we demonstrate elimination-induced under conditions extended network polymers.

Language: Английский

Citations

2