MISC

査読有り
2004年

Direct catalytic asymmetric Mannich-type reaction of hydroxyketone using a Et<inf>2</inf>Zn/linked-BINOL complex: Synthesis of either anti- or syn-β-amino alcohols

Journal of the American Chemical Society
  • Shigeki Matsunaga
  • ,
  • Takamasa Yoshida
  • ,
  • Hiroyuki Morimoto
  • ,
  • Naoya Kumagai
  • ,
  • Masakatsu Shibasaki

126
28
開始ページ
8777
終了ページ
8785
記述言語
英語
掲載種別
DOI
10.1021/ja0482435

Full details of a direct catalytic asymmetric Mannich-type reaction of a hydroxyketone using a Et2Zn/(S,S)-linked-BINOL complex are described. By choosing the proper protective groups on imine nitrogen, either anti- or syn-β-amino alcohol was obtained in good diastereomeric ratio, yield, and excellent enantiomeric excess using the same zinc catalysis. N-Diphenylphosphinoyl (Dpp) imine 3 gave anti-β-amino alcohols in anti/syn = up to &gt;98/2, up to &gt;99% yield, and up to &gt;99.5% ee, while Boc-imine 4 gave syn-β-amino alcohols in anti/syn = up to 5/95, up to &gt;99% yield, and up to &gt;99.5% ee. The high catalyst turnover number (TON) is also noteworthy. Catalyst loading was successfully reduced to 0.02 mol % (TON = up to 4920) for the anti-selective reaction and 0.05 mol % (TON = up to 1760) for the syn-selective reaction. The Et2Zn/(S,S)-linked-BINOL complex exhibited far better TON than in previous reports of catalytic asymmetric Mannich-type reactions. Mechanistic studies to clarify the reason for the high catalyst efficiency as well as transformations of Mannich adducts are also described.

Web of Science ® 被引用回数 : 159

リンク情報
DOI
https://doi.org/10.1021/ja0482435
PubMed
https://www.ncbi.nlm.nih.gov/pubmed/15250731
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000222704700054&DestApp=WOS_CPL
URL
http://www.scopus.com/inward/record.url?eid=2-s2.0-3242668608&partnerID=MN8TOARS
ID情報
  • DOI : 10.1021/ja0482435
  • ISSN : 0002-7863
  • ORCIDのPut Code : 26455444
  • PubMed ID : 15250731
  • SCOPUS ID : 3242668608
  • Web of Science ID : WOS:000222704700054

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