Abstract
Methodologies with chiral enolates including the stereoselective construction of the quaternary carbon, rearrangement of the vinylketene N,O-acetals, the remote stereoinduction with vinylketene silyl N,O-acetals, and the construction of 1,2-diols having the tertiary alcohol have been developed to apply to the natural product synthesis. Each isomer at the quaternary carbon has been synthesized from one enantiomer of α,β-unsaturated imide by choosing whether alkylation of the dienolate anion or rearrangement of the vinylketene N,O-acetal with MeAlCl2. The vinylketene silyl N,O-acetals possessing the chiral auxiliary reacted with aldehydes in the presence of TiCl4 to realize the stereocontrol at the y and 8 positions. Aldol reactions with lactate having the chiral auxiliary provided the 1,2-diols possessing the tertiary alcohol. The major stereoisomer depended on the chiral auxiliary and the protective group on the hydroxy group of lactate. These methodologies realized the short-step syntheses of natural products.
Original language | English |
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Pages (from-to) | 24-37 |
Number of pages | 14 |
Journal | Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry |
Volume | 67 |
Issue number | 1 |
DOIs | |
Publication status | Published - 2009 Jan |
Keywords
- Aldol reaction
- Enolate
- Ketene N,O-acetal
- Natural product
- Oxazolidinone
- Quaternary carbon
- Tertiary alcohol
- Total synthesis
- Vinylogous mukaiyama aldol reaction
ASJC Scopus subject areas
- Organic Chemistry