Chiroptical inversion induced by sandwiching units in chiral polythiourethane

Nagai, Atsushi; Ochiai, Bungo; Endō, Takeshi

doi:10.1039/b600417b

Cited by 5 publications

(4 citation statements)

References 19 publications

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“…It took more than 40 years, until when it was explicitly reported the living ring‐opening polymerization of an optically active cyclic thiourethane derived from l ‐serine by methyl trifluoromethanesulfonate (TfOMe) in 0.5 m DCM at 30 °C. The resulting chiral polythiourethane (as shown in Scheme A) was isolated in quantitative yield with head‐to‐tail structure and narrow molecular weight distribution ( Đ < 1.14) . The fact that polymer was optically active had been confirmed by the specific rotation of −233.3° at a M n of 13.300 g·mol −1 .…”

Section: Chemistrymentioning

confidence: 94%

Sulfur Chemistry in Polymer and Materials Science

Mutlu

Ceper

et al. 2018

Macromol. Rapid Commun.

278

220

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The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/marc.201800650. ChemistryBefore moving to the recent advances within the last 5 years in the diverse applications of sulfur chemistry in polymer and Sulfur-Containing PolymersSulfur and its functional groups are major players in an area of exciting research taking place in modern polymer and materials science, both in academia and industry. In fact, manifold sulfur-based reactions that are both exceptionally versatile as well as tremendously useful have been implemented, and further utilized for the design and preparation of polymeric materials that lead to a plethora of applications ranging from medicine to optics and nanotechnology to separation science. Hence, within this review, an overview of strategies and developments used over the last 5 years to reinforce the importance of the sulfur functional group in modern polymer and materials science is presented. In particular, many important references in the primary literature of sulfur chemistry are referred to, including thiol-ene, thiol-yne, thiol-Michael addition, disulfide cross-linking, and thiol-disulfide exchange, among others, by explaining and illustrating the important principles. Last but not least, the grand aim to underpin the importance of sulfur in modern polymer and materials science is achieved by presenting selected examples in diverse fields and postulating the respective potential for real-world applications. he is now a full professor at KIT.sulfur atoms, and tetraphenylethene-bearing di(alkyl bromide) (Scheme 3). The yield of the polymerization was dependent on the di(alkyl bromide) monomer; the longer spacer between the aromatic moiety and the reactive bromide end groups Scheme 1. The discussion henceforth focuses on the synthesis of polymers possessing the depicted sulfur functional groups. Scheme 2.Representative examples of polythioethers prepared via A) the nucleophilic substitution reaction between an electrophilic dihalide with nucleophilic derivatives of dithiols under alkaline conditions; B) the thiol-ene/yne addition reaction between AA and BB type monomers (i.e., dithiols and dienes/diynes); and C) radical or ionic ring-opening of sulfurcontaining strained rings.Scheme 3. The thiol-bromo polymerization of conformationally fixed monomers to provide multifunctional polymers. [19] Macromol. Rapid Commun. 2019, 40, 1800650 Scheme 4. The regioselective selective nucleophilic aromatic substitution between thiol and fluorinated aromatic compounds, the para-fluorothiol reaction (PFTR).Scheme 5. Synthesis of a linear polymer via PFTR-reaction. [21]

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Section: Chemistrymentioning

confidence: 94%

Sulfur Chemistry in Polymer and Materials Science

Mutlu

Ceper

et al. 2018

Macromol. Rapid Commun.

278

220

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“…However, most of the developed systems are characterized by structural complexity and/or demanding synthetic methodologies toward their preparation. Moreover, a limited number of reports appear in the literature dealing with the synthesis of well‐defined optically active polymers characterized by predetermined molecular weights (MWs) and narrow molecular weight distributions (MWDs) 23–31. The aforementioned characteristics are highly desirable, as they allow for their structural characteristics to be correlated to the properties of the materials.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of well‐defined optically active methacrylic diblock copolymers

Achilleos

Kafouris

Holder

et al. 2012

J. Polym. Sci. A Polym. Chem.

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A new, simple, and cost-effective approach toward the development of well-defined optically active diblock copolymers based on methacrylate monomers is described for the first time. Starting from the low-cost optically active (S)-(À)-2-methyl-1-butanol, a new optically active methacrylic monomer, namely, (S)-(þ)-2-methyl-1-butyl methacrylate [(S)-(þ)-MBuMA], was synthesized. Reversible addition fragmentation chain transfer polymerization was then used for preparing well-defined poly[(S)-(þ)-MBuMA] homopolymers and watersoluble diblock copolymers based on [(S)-(þ)-MBuMA] and the hydrophilic and ionizable monomer 2-(dimethyl amino)ethyl methacrylate (DMAEMA). The respective homopolymers and diblock copolymers were characterized in terms of their molecular weights, polydispersity indices, and compositions by size exclusion chromatography and 1 H NMR spectroscopy. Polarim-etry measurements were used to determine the specific optical rotations of these systems. The structural and compositional characteristics of micellar nanostructures possessing an optically active core generated by p((S)-(þ)-MBuMA)-b-p(DMAEMA) chains characterized by predetermined molecular characteristics may be easily tuned to match biological constructs. Consequently, the aggregation behavior of the p[(S)-(þ)-MBuMA]-bp[DMAEMA] diblock copolymers was investigated in aqueous media by means of dynamic light scattering and atomic force microscopy, which revealed the formation of micelles in neutral and acidified aqueous solutions. V C 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: [4215][4216][4217][4218][4219][4220][4221][4222] 2012

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“…Moreover, the separation of the solid acids from the concentrated sulfuric acid is a difficult operation. Polythiourethane was one of the most important polymers that are wide used as optical materials because of their high refractive indexes 11–12. The polythiourethane could own some free SH groups, which could be transformed to sulfonic acid groups easily.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of a novel polythiourethane‐based acid and its catalytic activity

Du¹,

Li²,

Sun³

et al. 2011

Asia-Pacific J Chem Eng

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Acid catalysts are very important in the production of many industrial chemicals. The novel polythiourethane-based solid acid has been synthesized via two steps. The copolymerization of tolylenediisocyanate (TDI) and 1,2-bis[(2-mercaptoethyl)thio]-3-mercapto-propane (MR) was carried out as the first step, and the amount of free mercarpto groups in the polythiourethane was controlled by adjusting the molar ratio of TDI and MR. The second step was the formation of the sulfonic acid groups by oxidation of the free mercapto groups. Possible catalytic activity was investigated through the traditional acid-catalyzed reactions including acetylation and synthesis of Schiff base. The results showed that this novel catalyst was very efficient for these reactions and produced high yields. Use of this catalyst simplifies process operations by not requiring any solvent, plus low usage amounts and low cost of the catalyst used with high yields, in particular, wide applicability and reusability are key features. The novel solid acid catalyst also has great potential for more environmental-friendly processes as it can be recycled and reused (easily separated) without any loss of activity. 

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Chiroptical inversion induced by sandwiching units in chiral polythiourethane

Abstract: Chiroptical behavior of a hydrogen-bond-regulated chiral polythiourethane segment was inversed by sandwiching sterically demanding segments in copolymers prepared by cationic ring-opening copolymerization of chiral cyclic thiourethanes derived from L-serine.

Cited by 5 publications

References 19 publications

Sulfur Chemistry in Polymer and Materials Science

Sulfur Chemistry in Polymer and Materials Science

Synthesis and characterization of well‐defined optically active methacrylic diblock copolymers

Synthesis of a novel polythiourethane‐based acid and its catalytic activity

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