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Helix-Sense-Selective Polymerization of 3,5-bis(hydroxymethyl)phenylacetylene Rigidly Bearing Galvinoxyl Residues and Their Chiroptical Properties

Four kinds of newly synthesized achiral phenylacetylenes bearing a phenylhydrogalvinoxyl residue at 4-position were polymerized by using a chiral rhodium catalyst system, [Rh(nbd)B(C(6)H(5))(4)] or [Rh(nbd)Cl](2) catalysts in the presence of chiral (R)-(+)- or (S)-(–)-1-phenylethylamine ((R)- or (S)...

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Autores principales: Shi, Zhichun, Wang, Jianjun, Teraguchi, Masahiro, Aoki, Toshiki, Kaneko, Takashi
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6918253/
https://www.ncbi.nlm.nih.gov/pubmed/31766269
http://dx.doi.org/10.3390/polym11111877
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author Shi, Zhichun
Wang, Jianjun
Teraguchi, Masahiro
Aoki, Toshiki
Kaneko, Takashi
author_facet Shi, Zhichun
Wang, Jianjun
Teraguchi, Masahiro
Aoki, Toshiki
Kaneko, Takashi
author_sort Shi, Zhichun
collection PubMed
description Four kinds of newly synthesized achiral phenylacetylenes bearing a phenylhydrogalvinoxyl residue at 4-position were polymerized by using a chiral rhodium catalyst system, [Rh(nbd)B(C(6)H(5))(4)] or [Rh(nbd)Cl](2) catalysts in the presence of chiral (R)-(+)- or (S)-(–)-1-phenylethylamine ((R)- or (S)-PEA) cocatalysts. Poly(m-HGDHPA) and poly(m-HGTHPA) in THF showed Cotton signals at the absorption regions of the main chain and hydrogalvinoxyl in the circular dichroism (CD) spectra. It indicated that excess of one-handed helical polyacetylene backbone was induced by helix-sense-selective polymerization (HSSP) under the asymmetric conditions despite the achiral monomer, and the hydrogalvinoxyl moieties were also arranged to form one-handed helical structure. However, there was no Cotton effect for poly(p-HGDHPA) and poly(p-HGTHPA) because the intramolecular hydrogen bonding did not act well to stabilize the helical conformation. The hydrogalvinoxyl units of poly(m-HGDHPA) and poly(m-HGTHPA) were converted to the corresponding galvinoxyl radicals after treatment with PbO(2). In the CD spectra of the polyradicals, the Cotton effects decreased depending on their static stability of helical conformation, suggesting that reversal conformation of the polymer chain arose.
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spelling pubmed-69182532019-12-24 Helix-Sense-Selective Polymerization of 3,5-bis(hydroxymethyl)phenylacetylene Rigidly Bearing Galvinoxyl Residues and Their Chiroptical Properties Shi, Zhichun Wang, Jianjun Teraguchi, Masahiro Aoki, Toshiki Kaneko, Takashi Polymers (Basel) Article Four kinds of newly synthesized achiral phenylacetylenes bearing a phenylhydrogalvinoxyl residue at 4-position were polymerized by using a chiral rhodium catalyst system, [Rh(nbd)B(C(6)H(5))(4)] or [Rh(nbd)Cl](2) catalysts in the presence of chiral (R)-(+)- or (S)-(–)-1-phenylethylamine ((R)- or (S)-PEA) cocatalysts. Poly(m-HGDHPA) and poly(m-HGTHPA) in THF showed Cotton signals at the absorption regions of the main chain and hydrogalvinoxyl in the circular dichroism (CD) spectra. It indicated that excess of one-handed helical polyacetylene backbone was induced by helix-sense-selective polymerization (HSSP) under the asymmetric conditions despite the achiral monomer, and the hydrogalvinoxyl moieties were also arranged to form one-handed helical structure. However, there was no Cotton effect for poly(p-HGDHPA) and poly(p-HGTHPA) because the intramolecular hydrogen bonding did not act well to stabilize the helical conformation. The hydrogalvinoxyl units of poly(m-HGDHPA) and poly(m-HGTHPA) were converted to the corresponding galvinoxyl radicals after treatment with PbO(2). In the CD spectra of the polyradicals, the Cotton effects decreased depending on their static stability of helical conformation, suggesting that reversal conformation of the polymer chain arose. MDPI 2019-11-13 /pmc/articles/PMC6918253/ /pubmed/31766269 http://dx.doi.org/10.3390/polym11111877 Text en © 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Shi, Zhichun
Wang, Jianjun
Teraguchi, Masahiro
Aoki, Toshiki
Kaneko, Takashi
Helix-Sense-Selective Polymerization of 3,5-bis(hydroxymethyl)phenylacetylene Rigidly Bearing Galvinoxyl Residues and Their Chiroptical Properties
title Helix-Sense-Selective Polymerization of 3,5-bis(hydroxymethyl)phenylacetylene Rigidly Bearing Galvinoxyl Residues and Their Chiroptical Properties
title_full Helix-Sense-Selective Polymerization of 3,5-bis(hydroxymethyl)phenylacetylene Rigidly Bearing Galvinoxyl Residues and Their Chiroptical Properties
title_fullStr Helix-Sense-Selective Polymerization of 3,5-bis(hydroxymethyl)phenylacetylene Rigidly Bearing Galvinoxyl Residues and Their Chiroptical Properties
title_full_unstemmed Helix-Sense-Selective Polymerization of 3,5-bis(hydroxymethyl)phenylacetylene Rigidly Bearing Galvinoxyl Residues and Their Chiroptical Properties
title_short Helix-Sense-Selective Polymerization of 3,5-bis(hydroxymethyl)phenylacetylene Rigidly Bearing Galvinoxyl Residues and Their Chiroptical Properties
title_sort helix-sense-selective polymerization of 3,5-bis(hydroxymethyl)phenylacetylene rigidly bearing galvinoxyl residues and their chiroptical properties
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6918253/
https://www.ncbi.nlm.nih.gov/pubmed/31766269
http://dx.doi.org/10.3390/polym11111877
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