Synthesis of poly(quinoxaline‐2,3‐diyl)s with alkoxy side chains by aromatizing polymerization of 4,5‐dialkoxy‐substituted 1,2‐ diisocyanobenzenes

Nagata, Yuuya; Suginome, Michinori

doi:10.1002/pola.24871

Cited by 9 publications

(4 citation statements)

References 47 publications

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“…Although the activity of the Ni complex is higher than that of the Pd complex, the screw-sense selectivity is lower (up to > 99% screw-sense excess). The Pd and Ni complexes with the optically active imidazoline group have been applied for screw-sense selective polymerization of various 1,2-diisocyanoarenes. − …”

Section: Transition Metal-catalyzed Cyclopolymerization Of Monomers O...mentioning

confidence: 99%

Cyclopolymerizations: Synthetic Tools for the Precision Synthesis of Macromolecular Architectures

2018

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Monomers possessing two functionalities suitable for polymerization are often designed and utilized in syntheses directed to the formation of cross-linked macromolecules. In this review, we give an account of recent developments related to the use of such monomers in cyclopolymerization processes, in order to form linear, soluble macromolecules. These processes can be activated by means of radical, ionic, or transition-metal mediated chain-growth polymerization mechanisms, to achieve cyclic moieties of variable ring size which are embedded within the polymer backbone, driving and tuning peculiar physical properties of the resulting macromolecules. The two functionalities are covalently linked by a "tether", which can be appropriately designed in order to "imprint" elements of chemical information into the polymer backbone during the synthesis and, in some cases, be removed by postpolymerization reactions. The two functionalities can possess identical or even very different reactivities toward the polymerization mechanism involved; in the latter case, consequences and outcomes related to the sequence-controlled, precision synthesis of macromolecules have been demonstrated. Recent advances in new initiating systems and polymerization catalysts enabled the precision syntheses of polymers with regulated cyclic structures by highly regio- and/or stereoselective cyclopolymerization. Cyclopolymerizations involving double cyclization, ring-opening, or isomerization have been also developed, generating unique repeating structures, which can hardly be obtained by conventional polymerization methods.

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Section: Transition Metal-catalyzed Cyclopolymerization Of Monomers O...mentioning

confidence: 99%

Cyclopolymerizations: Synthetic Tools for the Precision Synthesis of Macromolecular Architectures

2018

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“…o-TolNiCl(PMe 3 ) 2 , 1 1,2-bis((S)-sec-butoxymethyl)-4,5-diisocyano-3,6-dimethylben--zene (Qa), 2 1,2-diisocyano-3,6-dimethyl-4,5-bis((S)-2-methylbutoxy)benzene (Qb), 3 1,2-diisocyano-3,6-dimethyl-4,5-bis((((S)-octan-2-yl)oxy)methyl)benzene (Qc), 4 1,2-di--isocyano-3,6-dimethyl-4,5-bis((((S)-octan-3-yl)oxy)methyl)benzene (Qd), 4 1,2-di--butoxy-4,5-diisocyano-3,6-dimethylbenzene (Q2), 5 1,2-diisocyano-3,6-dimethyl-4,5bis(propoxymethyl)benzene (Q3), 6 and (2',3'-diisocyano-4'-methyl-[1,1'-biphenyl]-2yl)diphenylphosphine sulfide (Qp), 7 1a(100), 8 1b(100), 8 1c(100), 8 1d(100), 8 2a(5/100), 9 2d(5/100), 9 3a(5/100), 9 3d(/100), 9 3d(2.5/97.5), 9 3d(5/95), 9 3d(7.5/92.5), 9 3d(10/90), 9 evaporated. The residue was subjected to preparative GPC to give 2b as a beige solid (29.4 mg, 93%).…”

Section: Generalmentioning

confidence: 99%

Solvent Effect on the Sergeants-and-Soldiers Effect Leading to Bidirectional Induction of Single-Handed Helical Sense of Poly(quinoxaline-2,3-diyl)s Copolymers in Aromatic Solvents

2016

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3d(15/85), 93d(20/80), 9 3d(40/60), 9 3d(60/40), 9 and 3d(80/20) 9 and dimethyl(1-bromonaphthalen-2-yl)phophonate (5) 10 were prepared according to the reported procedures. 4-Methyl-1-naphthaleneboronic acid (6) and other chemical reagents were purchased from the commercial sources and were used without further purification. Experimental Procedures and Spectral Data for New CompoundsSynthesis of Polymer 2b(5/100): Qb (1.64 mg, 5.0 µmol) and Q2 (30.04 mg, 100.0 µmol) were dissolved in THF (2 mL). A THF solution of o-TolNiCl(PMe 3 ) 2 (6.43 mM, 156 µL, 1.0 µmol) was added to the monomer solution with vigorous stirring. After 16 h, NaBH 4 (7.94 mg, 210 µmol) was added to the reaction mixture and stirred for 1 h. Water (10 mL) was added to the solution and extracted with CH 2 Cl 2 (15 ml). The organic extract was washed with brine (10 mL), dried over Na 2 SO 4 , and the solvent was

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“…Meanwhile, Ni complexes have been widely used for the polymerization of isocyanides because of their low cost, easy handling, and high activity. Deming and Novak succeeded in the living polymerization of alkyl isocyanides for the first time by using the π-allyl Ni complex in noncoordinating solvents. , A few decades later, Suginome and co-workers demonstrated that aryl Ni(II) complexes are suitable initiators for synthesizing helically chiral poly(aryl isocyanide)s and poly(quinoxaline-2,3-diyl)s − in a living manner. Recently, a nucleophile adduct of the tetra( tert -butylisocyano)Ni(II) complex was reported as an excellent initiator for the living polymerization of electron-poor aryl isocyanides .…”

Section: Introductionmentioning

confidence: 99%

Fast Living Polymerization of Challenging Aryl Isocyanides Using an Air-Stable Bisphosphine-Chelated Nickel(II) Initiator

2018

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Here we report a highly efficient living polymerization of challenging electron-rich or sterically hindered aryl isocyanides using an air-stable, but highly active, bisphosphinechelated nickel(II) complex. Initially, the living character was examined by screening various Ni(II) complexes, and we identified o-Tol(dppe)NiCl as an excellent initiator for the living polymerization of aryl isocyanides. On the basis of chain extension experiments and in situ 31 P NMR spectroscopy, we concluded that the high stability of the propagating species due to the tightly bound chelating ligand was crucial for successful living polymerizations. Not only reactive electron-poor aryl isocyanides but also more challenging electron-rich or sterically hindered aryl isocyanides underwent fast living polymerizations to give polymers having controlled M n with narrow dispersity. In addition, we confirmed that the electronic character of the monomer significantly affected the polymerization efficiency by comparing the polymerization of 4-octyloxyphenyl isocyanide and 3octyloxyphenyl isocyanide, which have the same substituents at different positions on the phenyl ring. Furthermore, ABCDE pentablock copolymer containing various substituents was efficiently synthesized in only 1 min.

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Synthesis of poly(quinoxaline‐2,3‐diyl)s with alkoxy side chains by aromatizing polymerization of 4,5‐dialkoxy‐substituted 1,2‐ diisocyanobenzenes

Cited by 9 publications

References 47 publications

Cyclopolymerizations: Synthetic Tools for the Precision Synthesis of Macromolecular Architectures

Cyclopolymerizations: Synthetic Tools for the Precision Synthesis of Macromolecular Architectures

Solvent Effect on the Sergeants-and-Soldiers Effect Leading to Bidirectional Induction of Single-Handed Helical Sense of Poly(quinoxaline-2,3-diyl)s Copolymers in Aromatic Solvents

Fast Living Polymerization of Challenging Aryl Isocyanides Using an Air-Stable Bisphosphine-Chelated Nickel(II) Initiator

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