- Hybrid monomer design for unifying conflicting polymerizability, recyclability, and performance properties
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Synthetic polymers have become indispensable for modern life and the global economy. However, the manufacturing and disposal of most of today's polymers follow a linear economy model, which has caused accelerated depletion of finite natural resources, severe worldwide plastics pollution, and enormous materials value loss. The design of future circular polymers considers closed-loop lifecycles toward a circular economy. A key challenge of this promising design includes innovation in monomer structure that could enable not only efficient polymerization to polymers with properties comparable to today's polymers but also selective depolymerization to recover the monomers with high yield and purity. However, these contrasting properties are conflicting in a single monomer structure. This work introduces a hybrid monomer design concept that hybridizes contrasting parent monomer structures to an offspring monomer that can unify conflicting (de)polymerizability and performance properties. Intrinsically recyclable polymers represent a circular economy approach to address plastics problems. However, the design of such circular polymers is challenged by unyielding trade-offs between the monomer's polymerizability and the polymer's depolymerizability and performance properties. Here, we introduce a hybrid monomer design strategy that synergistically couples a high ceiling temperature (HCT) sub-structure for high polymerizability and performance properties with a low ceiling temperature (LCT) sub-structure for high depolymerizability and recyclability within the same monomer structure. Thus, structural hybridization between HCT ε-caprolactone and LCT γ-butyrolactone led to an offspring [3.2.1]bicyclic lactone, which exhibits both high polymerizability and depolymerizability, otherwise conflicting properties in a typical monomer. The resulting polymer becomes a high-performance material, and thermal transition temperatures are ~200°C higher and tensile modulus 10× higher than its parent polymers. These results demonstrate that the HCT/LCT hybrid monomer strategy is a powerful approach for designing circular polymers where conflicting properties must be exploited and unified. Hybrid monomer design is shown to be a powerful approach to develop robust circular plastics without yielding to common property trade-offs by hybridizing parent monomer structures to an offspring monomer that can unify conflicting (de)polymerizability and performance properties.
- Caporaso, Lucia,Cavallo, Luigi,Chen, Eugene Y.-X.,Falivene, Laura,Li, Zi-Chen,Shi, Changxia
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- Discovery of an Oxycyclohexyl Acid Lysophosphatidic Acid Receptor 1 (LPA1) Antagonist BMS-986278 for the Treatment of Pulmonary Fibrotic Diseases
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The oxycyclohexyl acid BMS-986278 (33) is a potent lysophosphatidic acid receptor 1 (LPA1) antagonist, with a human LPA1 Kb of 6.9 nM. The structure-activity relationship (SAR) studies starting from the LPA1 antagonist clinical compound BMS-986020 (1), which culminated in the discovery of 33, are discussed. The detailed in vitro and in vivo preclinical pharmacology profiles of 33, as well as its pharmacokinetics/metabolism profile, are described. On the basis of its in vivo efficacy in rodent chronic lung fibrosis models and excellent overall ADME (absorption, distribution, metabolism, excretion) properties in multiple preclinical species, 33 was advanced into clinical trials, including an ongoing Phase 2 clinical trial in patients with lung fibrosis (NCT04308681).
- Cheng, Peter T. W.,Kaltenbach, Robert F.,Zhang, Hao,Shi, Jun,Tao, Shiwei,Li, Jun,Kennedy, Lawrence J.,Walker, Steven J.,Shi, Yan,Wang, Ying,Dhanusu, Suresh,Reddigunta, Ramesh,Kumaravel, Selvakumar,Jusuf, Sutjano,Smith, Daniel,Krishnananthan, Subramaniam,Li, Jianqing,Wang, Tao,Heiry, Rebekah,Sum, Chi Shing,Kalinowski, Stephen S.,Hung, Chen-Pin,Chu, Ching-Hsuen,Azzara, Anthony V.,Ziegler, Milinda,Burns, Lisa,Zinker, Bradley A.,Boehm, Stephanie,Taylor, Joseph,Sapuppo, Julia,Mosure, Kathy,Everlof, Gerry,Guarino, Victor,Zhang, Lisa,Yang, Yanou,Ruan, Qian,Xu, Carrie,Apedo, Atsu,Traeger, Sarah C.,Cvijic, Mary Ellen,Lentz, Kimberley A.,Tirucherai, Giridhar,Sivaraman, Lakshmi,Robl, Jeffrey,Ellsworth, Bruce A.,Rosen, Glenn,Gordon, David A.,Soars, Matthew G.,Gill, Michael,Murphy, Brian J.
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p. 15549 - 15581
(2021/11/16)
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- RECYCLABLE POLYMERS BASED ON RING-FUSED GAMMA-BUTYROLACTONES
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The invention discloses a class of new polymers, trans-ring-fused poly(4-hydroxybutyrate)s (RF-P4HB) that exhibit a unique set of properties, including robust thermal stability and mechanical strength, quantitative recyclability to the building block monomers via thermolysis and/or chemical catalysis, and convenient production from the chemical ring-opening polymerization under ambient temperature and pressure. Another unique property is the formation of crystalline stereocomplexed polymers with high melting temperature upon mixing the two enantiomeric RF-P4HB chains via stereocomplexing co-crystallization. This invention also provides the corresponding ring-fused lactone monomer structures that enable the synthesis of the RF-P4HB polymers, through trans-fusing of rings to the parent γ-butyrolactone ring. Furthermore, a polymerization or copolymerization process for the synthesis of RF-P4HB polymers and copolymers is disclosed.
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Page/Page column 34; 44; 48
(2020/02/23)
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- Calcium(II)- And Triflimide-Catalyzed Intramolecular Hydroacyloxylation of Unactivated Alkenes in Hexafluoroisopropanol
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We report an efficient intramolecular hydroacyloxylation of unactivated alkenes, offering a streamlined access to relevant γ-lactones, which features the utilization of either a calcium(II) salt or triflimide as a catalyst in hexafluoroisopropanol. This method could be applied to the synthesis of natural products and the late-stage functionalization of natural and bioactive molecules. Additionally, DFT computations were used to elucidate the twist of reactivity observed between the hydroamidation and hydroacyloxylation of unactivated alkenes regarding the formation of 5- and 6-membered rings.
- Qi, Chenxiao,Yang, Shengwen,Gandon, Vincent,Leb?uf, David
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supporting information
p. 7405 - 7409
(2019/10/02)
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- 1- (1-CYCLOHEXYL-4-PIPERIDINYL) -1, 3-DIHYDRO-2H-BENZIMIDAZOL-2-ONE DERIVATIVES WHICH HAVE ACTIVITY ON THE M1 RECEPTOR AND THEIR USE IN MEDICINE
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Compounds of formula (I) or a salt thereof are provided, wherein R4, R5, R6, Q and R are as defined in the description. Uses of the compounds as medicaments and in the manufacture of medicaments for treating psychotic disorders and cognitive impairments are disclosed. The invention further discloses pharmaceutical compositions comprising the compounds.
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Page/Page column 49-50
(2008/12/04)
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- Total synthesis of leustroducsin B
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(Chemical Equation Presented) Leustroducsin B was synthesized via a convergent route based on division of the leustroducsin molecule into three segments A, B, and C. Two coupling reactions (Julia coupling reaction and Nozaki-Hiyama-Kishi (NHK) reaction) w
- Miyashita, Kazuyuki,Tsunemi, Tomoyuki,Hosokawa, Takafumi,Ikejiri, Masahiro,Imanishi, Takeshi
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p. 5360 - 5370
(2008/12/21)
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- Total synthesis of leustroducsin B via a convergent route
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Total synthesis of leustroducsin B was achieved via a convergent route, which includes Julia coupling reaction of segment A with segment B followed by Stille coupling reaction of segment C.
- Miyashita, Kazuyuki,Tsunemi, Tomoyuki,Hosokawa, Takafumi,Ikejiri, Masahiro,Imanishi, Takeshi
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p. 3829 - 3833
(2008/02/07)
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- METHOD FOR THE PREPARATION OF ENANTIOMER FORMS OF CIS-CONFIGURED 3-HYDROXYCYCLOHEXANE CARBOXYLIC ACID DERIVATIVES USING HYDROLASES
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The present invention relates to a process for preparing chiral non-racemic cis-configured cyclohexanols or cyclohexanol derivatives of the formula (I) Cis-configured hydroxyl-cyclohexane carboxylic acid derivatives of formula (I) are central building blo
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Page/Page column 20
(2008/06/13)
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- Oxidative Decarboxylation of Cyclohexane Monocarboxylic Acid as a Degenerate Branching Chain Reaction. I. Kinetics
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Kinetics of product accumulation during the oxidative decarboxylation of cyclohexane monocarboxylic acid has been followed by GCMS, inhibitor and chemiluminescence methods.Results indicate that in the degenerate branching chain process selective (peroxy) radicals abstract predominantly tertiary hydrogen atoms from the substrate while non-selective (e.g. hydroxyl, alkoxy) radicals attack also secondary hydrogen atoms.The rate constant of the chain propagation was found to be kp = 7.5*106 exp (-57.6 kJ mol-1/RT) l mol-1 s-1.Furthermore it has been established, that the oxidative decarboxylation proceeds via two parallel pathways: one resulting in cyclohexanone, while the other avoiding the formation of the latter. Key Words: Chemical Kinetics / Elementary Reactions / Radicals / Oxidation, decarboxylation
- Nemes, I.,Heberger, K.,Keszler, A.,Vasvari, G.,Gal, D.,et al.
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- The vibrational spectra (100-1500 cm-1) of a series of bicyclooctanes assigned by means of scaled 3-21G ab initio harmonic force fields
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The infrared absorption (vapor phase and solution) and Raman (liquid phase) spectra of bicyclooctane, 8-oxabicyclooctane, 6-oxabicyclooctane, 6,8-dioxabicyclooctane, and the 7,7-dideutero-substituted derivatives of the last two compounds are reported in the region 100-1500 cm-1 for the first time.The vibrational spectra are assigned almost completely with the guidance of ab initio 3-21G geometries and scaled force fields.A total of 14 force-field scale factors are transferred from smaller molecules, predicting the frequencies with an average error of 7.6 cm-1 (1.2percent) for 196 assigned transitions.After optimizing the factors in an overlay refinement involving all six molecules, the frequencies are within 5.7 cm-1 (0.75percent) of experiment.The ab initio absorption and Raman intensities are calculated with the 3-21G basis set and are demonstrated to be of such accuracy as to be useful for the spectral assignments.These intensities are calculated with uniformly and nonuniformly scaled force fields and compared to the experimental spectra.The intensities derived from the latter force fields are superior, meaning that nonuniform scaling is preferable at this level of theory for both vibrational frequencies and normal mode descriptions.
- Eggimann, Thomas,Ibrahim, Nan,Shaw, R. Anthony,Wieser, Hal
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p. 578 - 610
(2007/10/02)
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- ORGANOSELENIUM-INDUCED CYCLIZATIONS IN ORGANIC SYNTHESIS
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A number of organoselenium reagents are introduced as efficient initiators of ring closures leading from unsaturated substrates to lactones, cyclic ethers, cyclic thioethers, N-heterocycles and carbocycles.These cyclizations often proceed with high ring selectivity and stereoselectivity and are accompained by the incorporation of the phenylseleno group (PheSe) into the final product.Methods are described for the effective removal of this group (PheSe) by oxidation or reduction achieving unsaturation or saturation.Finally the successful application of this Se-based methodology to the synthesis of stable and biologically active prostacyclins is outlined.Representative experimental procedures are included.
- Nicolaou, K.C.
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p. 4097 - 4109
(2007/10/02)
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