ChemInform Abstract: Chiral Dienolate-Based Remote Asymmetric Induction: The Asymmetric α-Oxylation/Pd(0)-Catalyzed Allylic Substitution Sequence Leading to γ-Chiral α,β-Unsaturated Acid Derivatives.

✍ Scribed by M. SUGIURA; Y. YAGI; S.-Y. WEI; T. NAKAI

• Publisher: John Wiley and Sons
• Year: 2010
• Weight: 44 KB
• Volume: 29
• Category: Article
• ISSN: 0931-7597
• DOI: 10.1002/chin.199836062

✦ Synopsis

The dienolates derived from the chiral imides (I) and (IV) undergo asymmetric α-oxylation with dibenzyl peroxydicarbonate to give the (E)-or (Z)-products (III) and (V) highly selectively. Both undergo thermal rearrangements to provide the γ-(S)-or γ-(R)-oxy-substituted derivatives with efficient asymmetric transmission. A similar efficiency is observed for a variety of Pd-catalyzed reactions with nucleophiles such as malonate, benzylalcohol, or tosylamide providing a series of γ-(S)-and γ-(R)-configurated products. -(SUGIURA,