Synthesis of polynorbornadienes by ring-opening metathesis polymerization and their saturated derivatives bearing various ester groups and carboxyl groups

Lin, Xiaoxue; Shi, Jianjun; Niwayama, Satomi

doi:10.1039/d2ra07779e

Cited by 5 publications

(3 citation statements)

References 47 publications

(44 reference statements)

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“…In addition, the method can control the molecular weight of the polymer and make the molecular weight distribution of the prepared polymer narrow [39,40]. Norbornene (NBE) is one of the most used monomers in ROMP polymerization [41][42][43], which provides excellent convenience for polymers to introduce functional groups. Our group also reported the synthesis of amphiphilic bottlebrush copolymers with an activated ester block and a PEG hydrophilic block via ROMP procedure using the monomers containing norbornene at the chain end.…”

Section: Introductionmentioning

confidence: 99%

Polymeric Micelles with Chiral Diamine-Ru(II) Catalysts for Asymmetric Transfer Hydrogenation of Ketones in Water

Zhou,

Ji,

Wang

et al. 2023

J Inorg Organomet Polym

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Chiral aromatic alcohols with unique structures have attracted wide attention in asymmetric catalysis for decades. In this study, polymeric micelles with chiral diamine-Ru(II) catalysts in the hydrophobic core for asymmetric transfer hydrogenation of ketones affording chiral aromatic alcohols were presented. Firstly, block polymers with (1R,2R)-(+)-1,2-diphenyl ethylenediamine (DPEN) in the branched chain were successfully synthesized by Ring-Opening Metathesis Polymerization (ROMP) using 1,1-dimethylethyl N-(2amino-1,2-diphenylethyl) carbamate (NB-DPEN-Boc) and polyethylene glycol (NB-PEG2000) with norbornene groups as raw materials. The structures of block polymers P(DPEN)-co-P(PEG2000) were characterized by FT-IR and 1 H NMR. Next, Block polymers with chiral DPEN ligand in the branched chain coordinate with [RuCl2(p-cymene)]2 to provide amphiphilic polymers with chiral diamine-Ru(II) catalyst.Then, the self-assembly of the amphiphilic polymers in water produced the polymeric micelles with chiral diamine-Ru(II) catalysts in the hydrophobic core. The particle sizes were found to be 65 nm by DLS analysis. The polymeric micelles as catalytic nanoreactors were successfully applied in the asymmetric transfer hydrogenation (ATH) of various ketones in water. The heterogenization of homogeneous catalysts and construction of catalysts for aqueous catalysis demonstrate potential application prospects in the preparation of chiral aromatic alcohols.

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Section: Introductionmentioning

confidence: 99%

Polymeric Micelles with Chiral Diamine-Ru(II) Catalysts for Asymmetric Transfer Hydrogenation of Ketones in Water

Zhou,

Ji,

Wang

et al. 2023

J Inorg Organomet Polym

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“…These reactions were among the first examples of water-mediated desymmetrization reactions. Half-esters produced in these reactions are very versatile building blocks applied to the synthesis of pharmaceuticals, natural products, and polymers. − These reactions can produce the corresponding half-esters even in near-quantitative yields in many cases.…”

Section: Introductionmentioning

confidence: 99%

Micellar Mechanisms for Desymmetrization Reactions in Aqueous Media

Niwayama,

Hiraga

2023

ACS Omega

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Water-mediated organic reactions significantly contribute to the protection of the environment. Desymmetrization reactions, which convert only one of the identical functional groups within one molecule, are cost-effective because of the low cost of the starting materials. In combination with these two merits, highly efficient and practical selective monohydrolysis reactions of symmetric diesters were previously reported. The products of these reactions are versatile building blocks. The mechanisms of this reaction are hypothesized to proceed through micellar aggregates in which the hydrophilic carboxylate anions formed by monohydrolysis are directed outward and the remaining hydrophobic groups are directed inward in governing the selectivities. Here, dynamic light scattering and electrophoretic light scattering experiments were performed for detection of the key intermediates in the reaction. These experiments revealed the existence of aggregates with negative charges on the surface in the mainly aqueous media, supporting the reaction mechanisms that control the high selectivities.

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“…In general, a typical SI-ROMP protocol contains three essential procedures, as demonstrated in Scheme a: (i) olefin groups are grafted to the surface covalently or noncovalently; (ii) metathesis catalysts are attached on the surface by reacting with the olefin bonds; (iii) monomers are grafted from the surface via ROMP. ,, Due to the living nature of ROMP mechanism, SI-ROMP is a living surface polymerization and can provide well controlled grafted chain with narrow polydispersity. ,− …”

Section: Introductionmentioning

confidence: 99%

Surface Chain-Transfer Ring-Opening Metathesis Polymerization

Wu,

Ren,

Tong

et al. 2023

Langmuir

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Ring-opening metathesis polymerization (ROMP) is a powerful method to graft various types of polymer chains to a given surface. While surface-initiated ROMP (SI-ROMP) serves as an efficient tool for surface modification and is therefore widely reported, the method requires grafting (1) the olefin substrate and (2) the metathesis catalyst to the surface prior to the polymerization with multiple synthetic and work up steps. To overcome this difficulty, we proposed the use of the chain-transfer reaction as an alternative method for surface modification. Terminal olefins are grafted to the surface without the need to graft the metathesis catalysts, and polymers with olefin backbones are polymerized and grafted simultaneously via both ROMP and chain transfer (cross-metathesis between olefins from backbones and surfaces). Compared to SI-ROMP, this surface-chain transfer ROMP (SC-ROMP) method avoids grafting the catalyst and growing polymer chains from the surface and could be achieved in a single step. Various types of surfaces like carbon nanotubes, carbon fibers, graphene nanosheets, and silica microspheres are used for demonstration. We envision that this work could bring a convenient and effective solution to surface modification via ROMP.

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Synthesis of polynorbornadienes by ring-opening metathesis polymerization and their saturated derivatives bearing various ester groups and carboxyl groups

Abstract: Polymer libraries were synthesized in a controlled living manner from half-esters efficiently prepared by the selective monohydrolysis of symmetric diesters.

Cited by 5 publications

References 47 publications

Polymeric Micelles with Chiral Diamine-Ru(II) Catalysts for Asymmetric Transfer Hydrogenation of Ketones in Water

Polymeric Micelles with Chiral Diamine-Ru(II) Catalysts for Asymmetric Transfer Hydrogenation of Ketones in Water

Micellar Mechanisms for Desymmetrization Reactions in Aqueous Media

Surface Chain-Transfer Ring-Opening Metathesis Polymerization

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