Chirality of polyvinyl compounds. 5. Optically active polymers with structural chirality in the main chain prepared through an asymmetric cyclocopolymerization

Wulff, Günter; R, Kemmerer; Vogt, Bettina

doi:10.1021/ja00258a032

Cited by 63 publications

(45 citation statements)

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“…Measurements. The 1 H (400 MHz) and 13 C NMR (100 MHz) spectra were recorded by a JEOL JNM-A400II instrument. Elemental analysis was conducted using a Yanaco CHN corder MT-6 (Center for Instrumental Analysis, Hokkaido University).…”

Section: Methodsmentioning

confidence: 99%

Enantiomer-Selective Radical Polymerization of Bis(4-vinylbenzoate)s with Chiral Atom Transfer Radical Polymerization Initiating Systems

et al. 2007

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We report a series of cyclopolymerizations of bis(4-vinylbenzoate) monomers through an atom transfer radical polymerization (ATRP) using chiral ligands. Cyclized polymers showing chiroptical properties were produced by polymerization of the racemic bifunctional monomer, rac-2,4-pentanediyl bis(4-vinylbenzoate) (rac-1), and enantiomerically unbalanced bifunctional monomers were recovered, providing substantial evidence for the enantiomer-selective polymerization of rac-1 mediated through the ATRP with chiral ligands. A comparison between the enantiomerically pure monomers, (2R,4R)-2,4-pentanediyl bis(4-vinylbenzoate) (RR-1) and (2S,4S)-2,4-pentanediyl bis(4-vinylbenzoate) (SS-1), revealed a drastic discrepancy in the rates of their homopolymerizations during the ATRP. The enantiomeric copolymerization of RR-1 and SS-1 indicated that the monomer reactivity ratio of RR-1 was higher than that of SS-1 for the ATRP with chiral ligands. The results of both homopolymerizations and copolymerizations clearly demonstrate the propensity for incorporation of the RR-1 enantiomer and thus the enantiomer-selective polymerization in this system. The monomer-structural effects on the enantiomer-selectivity were examined, and it was concluded that the chirality in the monomer is also essential for the enantiomer-selective polymerization as well as the chiral ligands for ATRP. Finally, the viability of the cyclopolymerization in the enantiomer-selective polymerization was proved using mono(4-vinylbenzoate) monomers incapable of cyclizing through the polymerization.

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Section: Methodsmentioning

confidence: 99%

Enantiomer-Selective Radical Polymerization of Bis(4-vinylbenzoate)s with Chiral Atom Transfer Radical Polymerization Initiating Systems

et al. 2007

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“…For example, free -radical copolymerization of 84 with styrene and the following removal of the chiral template moiety from the obtained copolymer led to polystyrene that showed optical activity of [ α ] 365 − 0.5 ° to 3.5 ° (Scheme 13.13 ) [138] . The optical activity was ascribed to chiral ( S , S ) -diad units generated in the polymer chain through the cyclopolymerization step [139] . Other different bifunctional monomers such as 85 [140] , 86 [141] , 87 [142] , and 88 [143] have been reported to promote this type of copolymerization with styrene.…”

Section: Methacrylatesmentioning

confidence: 99%

Asymmetric Polymerization

Ito¹,

Nozaki²

2010

Catalytic Asymmetric Synthesis

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“…3. CD spectra of copolymers of M1 with M2 (3), M3 (4), M4 (2) and M5 (1) after removal of the template measured in dioxandwater 9 : 1 (v/v) in a 0,5-mm cuvette. The ordinate gives the specific ellipticity in deg .…”

Section: Tab 3 Subsequent Removal Of the Template)mentioning

confidence: 99%

On the chirality of polyvinyl compounds, 16. Optical activity of copolymers consisting of distyryl diads alternating with substituted maleimide or maleic anhydride units

Wulff

Krieger

1994

Macro Chemistry & Physics

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The copolymerization of 3,4-O-cyclohexylidene-~-mannitol i,2 : 5,6-bis-O-[(4-vinylphenyl)-boronate] (Ml) with different N-substituted maleimides and with maleic anhydride has been studied. These monomers copolymerize in i : 1 proportion, yielding after removal of the template (3,4-O-cyclohexylidene-~-mannitol) copolymers with bis(4-vinylphenylboronic acid) diads alternating with the other comonomeric unit. By deboronation these diads can be transformed to distyryl diads. These diads possess predominantly (S,S)-configuration; thus optically active copolymers with main-chain chirality were produced. The chiroptical properties (optical rotation and circular dichroism) of the copolymers were studied. Corresponding copolymers with maleic anhydride units can easily be transformed by polymer analogous reaction with nucleophiles, as was exemplified by alcoholysis with fatty alcohols.

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Chirality of polyvinyl compounds. 5. Optically active polymers with structural chirality in the main chain prepared through an asymmetric cyclocopolymerization

Cited by 63 publications

References 0 publications

Enantiomer-Selective Radical Polymerization of Bis(4-vinylbenzoate)s with Chiral Atom Transfer Radical Polymerization Initiating Systems

Enantiomer-Selective Radical Polymerization of Bis(4-vinylbenzoate)s with Chiral Atom Transfer Radical Polymerization Initiating Systems

Asymmetric Polymerization

On the chirality of polyvinyl compounds, 16. Optical activity of copolymers consisting of distyryl diads alternating with substituted maleimide or maleic anhydride units

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