Ring-opening metathesis polymerization of N-substituted-5-norbornene-2,3-dicarboximides in the presence of chiral additives

Mizuta, Kenichi; Fukutomi, Satoko; Yamabuki, Kazuhiro; Onimura, Kenjiro; Oishi, Tsutomu

doi:10.1038/pj.2010.38

Cited by 8 publications

(4 citation statements)

References 18 publications

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“…The system was calibrated using narrow polystyrene standards (800 ≤ M n ≤ 3 000 000 g/mol). Mo(N-Ad)(CHCMe 2 Ph)(OTf) 2 (DME), Mo(N-2- t BuPh)(CHCMe 2 Ph)(OTf) 2 (DME), and Mo(N-2,6-Me 2 Ph)(CHCMe 2 Ph)(OTf) 2 (DME) were prepared according to literature procedures. , Complexes I1 , I2 , I3 , I6 , I7 , I8 , I9 , I10 , I11 , I12 , I13 , I14 , I16 , and I30 and monomers M1 , M3 , M4 , M6 , M7 , and M8 were prepared according to literature procedures.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of trans-Isotactic Poly(norbornene)s through Living Ring-Opening Metathesis Polymerization Initiated by Group VI Imido Alkylidene N-Heterocyclic Carbene Complexes

et al. 2019

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The selectivity of several molybdenum and tungsten imido alkylidene N-heterocyclic carbene (NHC) complexes in the ring opening metathesis polymerization (ROMP) of enantiomerically pure endo,exo-2,3-dicarbomethoxynorborn-5-ene (DCMNBE) was examined by 1H- and 13C NMR spectroscopy. With one exception, all complexes showed a strong bias toward the formation of trans-isotactic polymers, some yielding polymers based on >98% trans-isotactic repeat units. This high selectivity was successfully extended to the ROMP of other monomers such as endo and exo-N-(R)-(+)-α-methylbenzyl-5-norbornene-2,3-dicarboximide, 2,3-bis[(menthyloxy)carbonyl]norbornadiene, and methyl-N-(S)-(−)-α-methylbenzyl-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate. The cationic initiators [Mo(NAr)(5 i Pr)(CHCMe2Ph)(X)][B(ArF)4] (Ar = 2- t BuC6H4, 2,6-Me2C6H3, 2,6- i Pr2C6H3; 5 i Pr = 1,3-diisopropylimidazol-2-ylidene; X = pyrrolide, O-2,6-(2,4,6-Me3C6H2)2C6H3; B(ArF)4 = B(3,5-(CF3)2C6H3)4) were found to be the most reactive ones, while also maintaining very high isoselectivity. Finally, a large imido ligand improved stereospecificity, while the choice of the NHC ligand had only a minor influence. Polymerizations can be terminated with 2-methoxystyrene, as evidenced by matrix-assisted laser-desorption time-of flight mass spectrometry.

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Section: Methodsmentioning

confidence: 99%

Synthesis of trans-Isotactic Poly(norbornene)s through Living Ring-Opening Metathesis Polymerization Initiated by Group VI Imido Alkylidene N-Heterocyclic Carbene Complexes

et al. 2019

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“…Substrates were additionally degassed by several freeze–pump–thaw cycles and stored over activated 4 Å molecular sieves. W(O)(CHCMe 2 Ph)Cl 2 (PMe 2 Ph) 2 ( P1 ), Mo( N -2,6-Me 2 -C 6 H 3 )(CHCMe 2 Ph)DME(OTf) 2 ·DME ( P2 ), Mo( N -2- t Bu-C 6 H 4 )(CHCMe 2 Ph)(OTf) 2 ·DME ( P3 ), AgB(Ar F ) 4 (MeCN) 3 , NaB(Ar F ) 4 , N -(2-bromophenyl)-2,6-di iso propylaniline ( L1 ), N -(2-(1 H -imidazol-1-yl)phenyl)-2,6-diisopropylaniline ( L2 ), tris(pentafluorophenyl)borane, M1 , M2 , M3 , and M4 were prepared according to the literature. Hydrogenated it -poly( M1 ) and it -poly( M3 ) were prepared on the basis of published procedures with certain modifications; hence, the synthesis of this polymer is reported below.…”

Section: Methodsmentioning

confidence: 99%

“…Substrates were additionally degassed by several freeze− pump−thaw cycles and stored over activated 4 Å molecular sieves. 48 and M4 49 were prepared according to the literature. Hydrogenated it-poly(M1) 40 and it-poly(M3) 41 were prepared on the basis of published procedures with certain modifications; hence, the synthesis of this polymer is reported below.…”

Section: ■ Conclusionmentioning

confidence: 99%

Olefin Metathesis and Stereoselective Ring-Opening Metathesis Polymerization with Neutral and Cationic Molybdenum(VI) Imido and Tungsten(VI) Oxo Alkylidene Complexes Containing N-Chelating N-Heterocyclic Carbenes

Bhattacharya,

Ziegler,

Wang

et al. 2024

Organometallics

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Neutral and cationic molybdenum(VI) imido and tungsten(VI) oxo alkylidene complexes containing an N-chelating N-heterocyclic carbene, W2) have been prepared. Catalysts Mo2, Mo4, W1, and W2 were characterized by single-crystal X-ray analysis. Catalysts Mo4 and W2 were benchmarked in homo-, cross-, ring-closing metathesis (RCM) as well as in ringopening cross-metathesis (ROCM) reactions. In the ring-opening metathesis polymerization (ROMP) of endo,exo-2,3dicarbomethoxynorborn-5-ene (DCMNBE), methyl-N-(S)-(−)-α-methylbenzyl-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate, exo-N-(R)-(+)-α-methylbenzyl-5-norbornene-2,3-dicarboximide, and 2,3-bis((menthyloxy)carbonyl)norbornadiene Mo4 and W2 offered access to trans-isotactic and cis-syndiotactic polymers, respectively.

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“…Advances in polymer chemistry over the last several decades have allowed alternative methods to access precise polyolefins through ring-opening metathesis polymerization (ROMP) − and acyclic diene metathesis polymerization (ADMET) − with some of them bearing phenyl substitutents. − Recently, we reported the synthesis of a unique alternating trimethylene–styrene copolymer that is inaccessible from ES systems . This system is a precision polyolefin that can be likened to an SBR or ESI (after backbone hydrogenation) with high S content (∼71% w/w) and a phenyl branch on exactly every fifth carbon along a linear backbone microstructure (Figure ).…”

Section: Introductionmentioning

confidence: 99%

Viscoelastic, Mechanical, and Glasstomeric Properties of Precision Polyolefins Containing a Phenyl Branch at Every Five Carbons

Kieber

Neary

Kennemur

2018

Ind. Eng. Chem. Res.

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Mechanical and viscoelastic properties of precision polyolefins, poly(4-phenylcyclopentene) (P4PCP) and its hydrogenated analog (H2-P4PCP) containing atactic phenyl branches at exactly every five carbons along the backbone are explored. Both materials are amorphous with a glass transition temperature of ∼17 ± 3 °C. Rheological investigations determined that P4PCP has an entanglement molar mass (M e = 10.0 kg mol–1) much higher and closer to polystyrene than H2-P4PCP (M e = 3.6 kg mol–1). Both materials have elastomeric and shape memory properties at ambient temperatures, which were further explored through strain hysteresis measurements. H2-P4PCP has an elastic recovery of ∼95% at max strain values up to 500% as determined by uniaxial tensile testing. Time–temperature superposition analysis, Williams–Landel–Ferry constants, and further mechanical analysis are discussed and compared to previously reported ethylene–styrene copolymers of similar phenyl-branch content within the microstructure.

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Ring-opening metathesis polymerization of N-substituted-5-norbornene-2,3-dicarboximides in the presence of chiral additives

Cited by 8 publications

References 18 publications

Synthesis of trans-Isotactic Poly(norbornene)s through Living Ring-Opening Metathesis Polymerization Initiated by Group VI Imido Alkylidene N-Heterocyclic Carbene Complexes

Synthesis of trans-Isotactic Poly(norbornene)s through Living Ring-Opening Metathesis Polymerization Initiated by Group VI Imido Alkylidene N-Heterocyclic Carbene Complexes

Olefin Metathesis and Stereoselective Ring-Opening Metathesis Polymerization with Neutral and Cationic Molybdenum(VI) Imido and Tungsten(VI) Oxo Alkylidene Complexes Containing N-Chelating N-Heterocyclic Carbenes

Viscoelastic, Mechanical, and Glasstomeric Properties of Precision Polyolefins Containing a Phenyl Branch at Every Five Carbons

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