スギウラ マサハル   Sugiura Masaharu
  杉浦 正晴
   所属   崇城大学  薬学部 薬学科
   崇城大学大学院  薬学研究科 薬学専攻
   職種   教授
言語種別 英語
発行・発表の年月 2001/12
形態種別 原著論文
査読 査読有り
標題 Lewis acid-catalyzed ring-opening reactions of semicyclic N,O-acetals possessing an exocyclic nitrogen atom: Mechanistic aspect and application to piperidine alkaloid synthesis
執筆形態 共著
掲載誌名 Journal of the American Chemical Society
掲載区分国外
巻・号・頁 123,pp.12510-12517
著者・共著者 M. Sugiura, H. Hagio, R. Hirabayashi, S. Kobayashi
概要 Ring-opening reactions of semicyclic N,O-acetals possessing an exocyclic nitrogen atom with silicon-based nucleophiles (silyl enol ethers, ketene silyl acetals, allylic silanes, and trimethylsilyl cyanide) were systematically studied for the first time. It was found that the reactions were effectively catalyzed by a Lewis acid, trimethylsilyl trifluoromethanesulfonate (TMSOTf), to afford 1,4- and 1,5-amino alcohols in high yields. In reactions of 3-oxygen functionalized semicyclic N,O-acetals, high 1,2-syn-diastereoselectivity was obtained. By 1H NMR experiment, the formation of the O-trimethylsilylated ring-opened product was observed as the initial product. These stereochemical outcomes can be rationalized by assuming four transition state models for the acyclic iminium ion intermediate. The synthetic utility of the reaction has been demonstrated in the diastereoselective synthesis of piperidine alkaloids, (+)-isofebrifugine and (±)-sedacryptine.
DOI 10.1021/ja0170448
ISSN 00027863
PMID 11741414
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