論文

2021年4月

Stereocontrolled radical polymerization of acrylamides by ligand-accelerated catalysis

Polymer Journal
  • Beomsu Park
  • ,
  • Yuji Imamura
  • ,
  • Shigeru Yamago

53
4
開始ページ
515
終了ページ
521
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1038/s41428-020-00444-0
出版者・発行元
SPRINGERNATURE

The role of alcohol in the Yb(OTf) - and Y(OTf) -catalyzed stereoselective radical polymerization of acrylamides is clarified. The coordination of an alcohol to the metal triflate generates a new complex, which increases both the polymerization rate and stereocontrol compared to those achieved by the metal triflate without an alcohol in the polymerization of N,N-diethylacrylamide. While the lanthanide triflate-catalyzed stereoselective polymerization of acrylamides in MeOH has already been well established synthetically, this is the first example that proves the formation of an alcohol-coordinated catalyst as the active catalyst. Job’s plot suggests that the stoichiometry between Yb(OTf) and MeOH in the complex is 1:2. The polymerization rate decreases slightly when MeOD is used instead of MeOH, with a secondary isotope effect of 1.14, strongly suggesting the importance of hydroxyl groups for increasing the reactivity. In contrast, no apparent secondary isotope effect is observed to affect the stereoselectivity. The chirality of the alcohol ligand does not affect the stereoselectivity, illustrating that the stereochemistry is most likely controlled by the penultimate effect, which has already been proposed. Furthermore, the conditions are highly compatible with those for organotellurium-mediated radical polymerization, and the dual control of molecular weight and tacticity is successfully achieved. 3 3 3

リンク情報
DOI
https://doi.org/10.1038/s41428-020-00444-0
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000598306000001&DestApp=WOS_CPL
Scopus
https://www.scopus.com/inward/record.uri?partnerID=HzOxMe3b&scp=85097501893&origin=inward
Scopus Citedby
https://www.scopus.com/inward/citedby.uri?partnerID=HzOxMe3b&scp=85097501893&origin=inward
ID情報
  • DOI : 10.1038/s41428-020-00444-0
  • ISSN : 0032-3896
  • eISSN : 1349-0540
  • SCOPUS ID : 85097501893
  • Web of Science ID : WOS:000598306000001

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