2021年3月
Asymmetric O-to-C aryloxycarbonyl migration of indolyl carbonates using single-handed dynamic helical polyquinoxalines bearing 4-aminopyridyl groups as chiral nucleophilic catalysts
Bulletin of the Chemical Society of Japan
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- 巻
- 94
- 号
- 3
- 開始ページ
- 943
- 終了ページ
- 949
- 記述言語
- 英語
- 掲載種別
- 研究論文(学術雑誌)
- DOI
- 10.1246/BCSJ.20200369
- 出版者・発行元
- CHEMICAL SOC JAPAN
Use of single-handed dynamic helical macromolecules as nucleophilic catalysts in asymmetric Steglich-type O-to-C aryloxycarbonyl rearrangement of 3-substituted indol-2-yl aryl carbonates is demonstrated. Among several single-handed poly-(quinoxaline-2,3-diyl) copolymers (PQXap) bearing achiral 4-aminopyridin-3-yl groups at the 5-position of the quinoxaline rings, PQXmdpp and PQXapy, containing N-methylpyrrolidine-fused pyridin-3-yl and 4-(1-azetidinyl)pyridin-3-yl groups, respectively, showed higher enantioselectivity and catalytic activity than PQXdmap, bearing 4-dimethylamino-pyridine-3-yl groups. Substrates bearing p-(trifluoromethyl)phenyloxycarbonyl groups on both the nitrogen and oxygen atoms showed high reactivity, giving oxindoles with a quaternary stereogenic carbon center at their 3-positions in up to 97:3 enantiomeric ratio in THF. The macromolecular catalysts underwent inversion of their helix sense by solvent effect, allowing the same catalyst to give the opposite enantiomer in a mixture of methyl t-butyl ether and 1,1,2-trichloroethane (3:1). The macromolecular catalysts could be easily recovered by adding acetonitrile to the reaction mixture and were reused four times without reduction in enantioselectivity.
- リンク情報
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- DOI
- https://doi.org/10.1246/BCSJ.20200369
- Web of Science
- https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000635201200007&DestApp=WOS_CPL
- Scopus
- https://www.scopus.com/inward/record.uri?partnerID=HzOxMe3b&scp=85104799539&origin=inward 本文へのリンクあり
- Scopus Citedby
- https://www.scopus.com/inward/citedby.uri?partnerID=HzOxMe3b&scp=85104799539&origin=inward
- ID情報
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- DOI : 10.1246/BCSJ.20200369
- ISSN : 0009-2673
- eISSN : 1348-0634
- SCOPUS ID : 85104799539
- Web of Science ID : WOS:000635201200007