Dewar Heterocycles as Versatile Monomers for Ring-Opening Metathesis Polymerization

Valence Isomerization ◽

Grubbs Catalysts ◽

Amino Acid Polymers ◽

Highly Strained ◽

Acetylene Derivatives ◽

Soluble Poly

We report the utility of readily available heterocycles as precursors to unique ring-opening metathesis polymerization (ROMP) monomers. Photochemical valence isomerization reactions of pyridones, dihydropyridines, and pyrones dearomatize the parent heterocycles to their highly strained Dewar isomers, which readily engage in controlled ROMP reactions using Grubbs catalysts. This strategy is used to access novel polymer backbones that contain strained β-lactam and azetidine cores, which can be further derivatized using post-polymerization chemistries. We demonstrate this through the synthesis of water-soluble β-amino acid polymers and soluble poly(acetylene) derivatives.

Synthesis of Organic and Water Soluble Poly(1,4-phenylenevinylenes) Containing Carboxyl Groups: Living Ring-Opening Metathesis Polymerization (ROMP) of 2,3-Dicarboxybarrelenes

Macromolecules ◽

10.1021/ma9701595 ◽

1997 ◽

Vol 30 (14) ◽

pp. 3978-3985 ◽

Cited By ~ 43

Author(s):

Michael W. Wagaman ◽

Robert H. Grubbs

Keyword(s):

Ring Opening ◽

Water Soluble ◽

Carboxyl Groups ◽

Soluble Poly

Stereospecific Synthesis of Poly(methylene-E-vinylene) by Ring Opening Metathesis Polymerization of Substituted Cyclopropene Using Grubbs Catalysts

Macromolecules ◽

10.1021/acs.macromol.9b01956 ◽

2019 ◽

Vol 52 (20) ◽

pp. 7749-7755 ◽

Cited By ~ 3

Author(s):

Jian-Jhih Peng ◽

Biswajit Panda ◽

Kamani Satyanarayana ◽

Hau-Ren Yang ◽

Shou-Ling Huang ◽

...

Keyword(s):

Ring Opening ◽

Stereospecific Synthesis ◽

Grubbs Catalysts

Diblock brush-arm star copolymers via a core-first/graft-from approach using γ-cyclodextrin and ROMP: a modular platform for drug delivery

Polymer Chemistry ◽

10.1039/c9py01146c ◽

2020 ◽

Vol 11 (2) ◽

pp. 541-550 ◽

Cited By ~ 1

Author(s):

Ruihan Li ◽

Xuesong Li ◽

Yipei Zhang ◽

Abigail O. Delawder ◽

Nathan D. Colley ◽

...

Keyword(s):

Drug Delivery ◽

Anticancer Drug ◽

Ring Opening ◽

Water Soluble ◽

Anticancer Drug Delivery ◽

Star Copolymers ◽

Modular Platform

Water-soluble diblock brush-arm star copolymers using γ-CD-based core-first ring-opening metathesis polymerization, allowing for anticancer drug delivery via host–guest interaction.

Soluble Poly(p-phenylenevinylene)s Through Ring-Opening Metathesis Polymerization

Synfacts ◽

10.1055/s-2006-955817 ◽

2007 ◽

Vol 2007 (2) ◽

pp. 0161-0161

Author(s):

M. Turner ◽

C.-Y. Yu

Keyword(s):

Ring Opening ◽

Soluble Poly

Alkyl substituted [2.2]paracyclophane-1,9-dienes

Organic & Biomolecular Chemistry ◽

10.1039/c6ob00885b ◽

2016 ◽

Vol 14 (25) ◽

pp. 6079-6087 ◽

Cited By ~ 16

Author(s):

Benjamin J. Lidster ◽

Dharam R. Kumar ◽

Andrew M. Spring ◽

Chin-Yang Yu ◽

Madeleine Helliwell ◽

...

Keyword(s):

Ring Opening ◽

Highly Strained

Highly strained alkyl-substituted [2.2]paracyclophane-1,9-dienes, suitable for ring opening metathesis polymerization to poly(phenylene vinylenes), have been prepared in excellent yields.

Surface-Initiated Ring-Opening Metathesis Polymerization (SI-ROMP): History, General Features, and Applications in Surface Engineering with Polymer Brushes

International Journal of Polymer Science ◽

10.1155/2021/6677049 ◽

2021 ◽

Vol 2021 ◽

pp. 1-15

Author(s):

Qingchuan Chen

Keyword(s):

Polymer Films ◽

Polymer Brushes ◽

Ring Opening ◽

Surface Engineering ◽

High Efficiency ◽

Microfluidic Channels ◽

Graphene Oxides ◽

Grubbs Catalysts

Surface-Initiated Ring-Opening Metathesis Polymerization (SI-ROMP) has attracted great attention in the past two decades because of its high efficiency in decorating material surfaces with functional polymer brushes. To fill the vacancy of review articles in SI-ROMP, this article is aimed at giving an overview of the history, the general features and procedures, and applications of SI-ROMP, guiding future researchers in this field. In general, SI-ROMP consists of three main steps: surface functionalization with olefin anchors, attachment of catalyst to the surface, and polymerization from the surface. Several metal-based catalysts for ROMP in solution have been developed, but most SI-ROMP reactions use the ruthenium-based Grubbs catalysts. SI-ROMP enables the rapid growth of polymer films on a large variety of substrates such as silica, gold, graphene oxides, carbon nanotubes, metal oxide nanowires, and composite polymer membranes. There are many methods to characterize these polymer brushes. In addition, some novel techniques have been developed to precisely control the surface polymer growth and lead to polymer films with unique structures and functions. Up to this day, SI-ROMP can be applied to the surface engineering of many novel materials, including ultrahydrophobic surfaces, microfluidic channels, electric devices, ion exchange media, and responsive surfaces.

Aggregation-induced emission block copolymers based on ring-opening metathesis polymerization

RSC Advances ◽

10.1039/c4ra08191a ◽

2014 ◽

Vol 4 (93) ◽

pp. 51194-51200 ◽

Cited By ~ 27

Author(s):

Yuming Zhao ◽

Ying Wu ◽

Guowei Yan ◽

Ke Zhang

Keyword(s):

Block Copolymers ◽

Self Assembly ◽

Ring Opening ◽

Water Soluble ◽

Amphiphilic Block Copolymers ◽

Aggregation Induced Emission ◽

Selective Solvents ◽

First Time

AIE amphiphilic block copolymers were developed from ROMP for the first time. By self-assembly in selective solvents, water soluble fluorescent nano-objects were prepared with varied structures including micelles and vesicles.