ChemInform Abstract: Catalytic Asymmetric Synthesis of Diarylacetates and 4,4-Diarylbutanoates. A Formal Asymmetric Synthesis of (+)-Sertraline.

✍ Scribed by Huw M. L. Davies; Douglas G. Stafford; Tore Hansen

• Publisher: John Wiley and Sons
• Year: 2010
• Weight: 36 KB
• Volume: 30
• Category: Article
• ISSN: 0931-7597
• DOI: 10.1002/chin.199942103

✦ Synopsis

Catalytic Asymmetric Synthesis of Diarylacetates and 4,4-Diarylbutanoates. A Formal Asymmetric Synthesis of (+)-Sertraline. -The Rh 2 ((S)-DOSP) 4 -catalyzed decomposition of aryldiazoacetates (I) and (IV) with cyclohexadiene (II) proceeds by insertion of the carbenoid into the allylic C-H bond to furnish (aryl)cyclohexadienylacetates [cf. (V)] with high asymmetric induction. The reaction of vinyldiazoacetates (VIIa)-(VIId) with cyclohexadiene (VIII) in the presence of the chiral rhodium catalyst unexpectedly affords 4-cyclohexadienylbutenoates (IXa)-(IXd) as formal C-H insertion-Cope rearrangement products in excellent stereoselectivity. This reaction can be successfully applied to the synthesis of 6-phenyl-4-cyclohexadienylhexadienoate (IXe) and the corresponding cyclohexylideneacetate (XI). Additionally, derivative (IXc) is shown to be a useful intermediate in the synthesis of the antidepressant (+)-sertraline (XII). -(