Stereospecific Anionic Polymerization of α-(N-tert-Butyl aminomethyl)acrylate Having Unprotected Amino Group

Habaue, Shigeki; Baraki, Hideo

doi:10.1295/polymj.29.872

Cited by 7 publications

(6 citation statements)

References 9 publications

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“…The 1 H NMR data were in good agreement with reported data (Habaue et al 1997 7, 14.0, 24.0, 24.4, 33.7, 36.4, 37.0, 44.4, 57.4, 61.6, 169.7 Isomerisation of alkyl 2-(bromomethyl)aziridines 14a-d to alkyl 3-…”

Section: Ethyl 2-[(tert-butylamino)methyl]acrylate (12a)supporting

confidence: 89%

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Synthesis of new functionalized aziridine-2- and azetidine-3-carboxylic acid derivatives of potential interest for biological and foldameric applications

et al. 2011

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A short synthesis of alkyl 2-(bromomethyl)aziridine-2-carboxylates and alkyl 3-bromoazetidine-3-carboxylates was developed involving amination, bromination and base-induced cyclization of alkyl 2-(bromomethyl)acrylates. The aziridines are the kinetically favored cyclization products and could be transformed into 3-bromoazetidine-3-carboxylic acid derivatives via thermal isomerization. The new small-membered azaheterocyclic α-and β-amino acid derivatives contain a bromo-substituted carbon center as a useful moiety for functionalization.Transformation of these functionalized azaheterocycles via nucleophilic substitution with carbon, sulfur, oxygen and nitrogen nucleophiles and via elaboration of the amino and carboxyl group provided a broad range of new conformationally constrained aziridine-2-and azetidine-3-carboxylic acid derivatives which are of interest from a biological point-of-view as well as for applications in the field of foldamers.

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Section: Ethyl 2-[(tert-butylamino)methyl]acrylate (12a)supporting

confidence: 89%

“…The synthesis of N-substituted alkyl 2-(aminomethyl)acrylates 12 via substitution reactions of alkyl 2-(bromomethyl)acrylates 11 with primary amines was performed under optimized conditions in analogy with literature procedures (Baraki et al 1999;Habaue et al 1997 hydrobromic acid in dichloromethane to the corresponding hydrobromide salts.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of new functionalized aziridine-2- and azetidine-3-carboxylic acid derivatives of potential interest for biological and foldameric applications

et al. 2011

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“…The polymer obtained from 1 with the Ph2NLi-TMEDA complex in toluene was isotactic (mm=83%), while that in THF, rich in syndiotacticity. 4 Therefore, the poly(3)s obtained in toluene must be highly isotactic. Although the 13 C NMR spectrum of carbonyl carbon in the polymer obtained with Ph 2 NLi in THF showed multi peaks with mostly different chemical shifts from that for highly isotactic poly(3) (Figure 3(c)), the 1 H NMR spectrum of the same polymer was assigned to a normal vinyl polymer structure corresponding to poly(3).…”

Section: Polymerization Of R:t-(n-alkylaminomethyl)acrylatesmentioning

confidence: 99%

“…We reported that the anionic polymerization of ethyl a-(N-t-butylaminomethyl)acrylate (1) having a reactive unprotected amino group with the lithium amide complexes such as the lithium diphenylamide complex with N,N,N' ,N' -tetramethylethylenediamine (Ph 2 NLi-TMEDA) in toluene afforded an isotactic polymer, while the polymerization in tetrahydrofuran (THF) gave a syndiotactic polymer. 4 The tacticity of the obtained polymer was fairly affected by the polarity of solvents and initiators. These results are quite different from those of the previously reported monomers, which have a polar substituent on the a-position of an acrylate.…”

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confidence: 97%

Stereospecific Anionic Polymerization and Novel Hydrogen-Transfer Polymerization of α-(Aminomethyl)acrylates Having Unprotected Amino Group

Baraki

Habaue

1999

Polym J

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ABSTRACT:Anionic polymerization of 1)(-(aminomethyl)acrylates (2-8) having an unprotected amino proton was carried out using lithium reagents at -78°C. Acrylates except for 4 and 8 afforded the polymers in good yields. The polymerization of ethyl 1)(-[N-(diphenylmethyl)aminomethyl]acrylate (3) with n-BuLi or the Ph2NLi-N,N,N',N'-tetramethylethylenediamine (TMEDA) complex in toluene afforded a polymer with a normal vinyl polymer structure and high isotacticity. Hydrogentransfer of the amino proton hardly occurred in the polymerization process. The anionic polymerizations of ethyl 1)(-[N-(1-phenylethyl)aminomethyl]acrylate (2) using lithium reagents in toluene and tetrahydrofuran (THF) proceeded with hydrogen-transfer reaction. CH carbon generated by hydrogen-transfer in the main chain was detected by DEPT NMR measurement of poly(2). The CH -containing unit in the polymer increased up to nearly 40% when THF was used as a solvent. Monomers 4 and 8 showed low polymerizability.

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“…Recently, we reported that the anionic polymerization of ␣-(alkoxymethyl)acrylates 1,2 and ␣-(aminomethyl)acrylates, [3][4][5] which have two different types of polar substituents, gave highly isotactic polymers with lithium reagents. In the course of these studies we found that highly isotactic poly[ethyl ␣-((S)-2-methoxymethyl-1-pyrrolidinylmethyl)acrylate] (poly(1)) showed [␣] 4 It has been reported that stereoregular arrangement of optically active groups along the backbone of vinyl polymers sometimes induces great enhancement of optical rotation of the polymers compared with that of the corresponding monomer.…”

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Stereospecific anionic polymerization of chiral benzyl ?-[(1-phenylethoxy)methyl]acrylate

Uno

Habaue

1998

Chirality

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A novel chiral monomer, benzyl α‐[(1‐phenylethoxy)methyl]acrylate was synthesized, and the stereoregularity and chiroptical property of the polymers obtained by radical and anionic polymerizations were investigated. Anionic polymerization in toluene provided a polymer with high isotacticity regardless of optical purity of the monomer and difference of counter cations, Li+ and Mg2+, while radical polymerization appears to yield an atactic polymer. The isotactic copolymers anionically obtained from a mixture of (R)‐ and (S)‐monomers showed peak splitting probably due to the triad arrangement of (R) and (S) groups of side chains in the resonance of 13C‐NMR spectra. The isotactic polymer prepared from enantiomerically pure (R)‐monomer ([α] 25 365 = +157°) with n‐BuLi in toluene exhibited higher specific rotation ([α] 25 365 = +262°) than that of the radical polymer ([α] 25 365 = +162°). This may be explained by regular arrangement of optically active groups along the polymer chain of the isotactic polymer. Chirality 10:711–716, 1998. © 1998 Wiley‐Liss, Inc.

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Stereospecific Anionic Polymerization of α-(N-tert-Butyl aminomethyl)acrylate Having Unprotected Amino Group

Cited by 7 publications

References 9 publications

Synthesis of new functionalized aziridine-2- and azetidine-3-carboxylic acid derivatives of potential interest for biological and foldameric applications

Synthesis of new functionalized aziridine-2- and azetidine-3-carboxylic acid derivatives of potential interest for biological and foldameric applications

Stereospecific Anionic Polymerization and Novel Hydrogen-Transfer Polymerization of α-(Aminomethyl)acrylates Having Unprotected Amino Group

Stereospecific anionic polymerization of chiral benzyl ?-[(1-phenylethoxy)methyl]acrylate

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