2009年
Aminolithiation of carbon-carbon double bonds as a powerful tool in organic synthesis
Pure and Applied Chemistry
- ,
- ,
- ,
- 巻
- 81
- 号
- 2
- 開始ページ
- 247
- 終了ページ
- 253
- 記述言語
- 英語
- 掲載種別
- 研究論文(国際会議プロシーディングス)
- DOI
- 10.1351/PAC-CON-08-08-02
A conjugate amination of α,β-unsaturated carbonyl compounds with lithium amides has become a powerful method of N-C bond-forming reactions. Chiral ligand-controlled asymmetric version of the conjugate amination of enoates was developed for practical bench chemistry, giving the enantioenriched amination product with over 99 % ee. In situ diastereoselective alkylation of resulting lithium enolates allowed us to form vicinal N-C and C-C bonds in a one-pot operation. This protocol enabled us to realize a short-step asymmetric synthesis of otamixaban key intermediate. Treatment of product 3-benzylamino- and 3-allylaminoesters with tert-butyllithium gave five- or seven-membered lactams through [1,2]- or [2,3]-rearrangement of intermediate β-lactams. Isolated C-C double bonds were also found to accept intramolecular aminolithiation affording the corresponding hydroamination products. Chiral lithiophilic ligand-catalyzed reaction gave enantioenriched hydroamination products with high ee. Stereoselective intramolecular aminolithiation of allylaminoalkenes was coupled with subsequent carbolithiation to give doubly cyclized product amines. © 2009 IUPAC.
- ID情報
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- DOI : 10.1351/PAC-CON-08-08-02
- ISSN : 0033-4545
- ISSN : 1365-3075
- SCOPUS ID : 61449114729