Chiral Nonracemic Pyridine Thiols and Thioethers Applied in Palladium-Catalyzed Allylic Substitution. An Example of Near-Perfect Enantioselection

Pyridine thiols and dithiols have been synthesized by base-induced addition of 2,6-lutidine to thiofenchone. These thiols were converted to their thioether derivatives by alkylation. Application of these compounds in palladium-catalyzed allylic substitution on 1,3-diphenylprop-2-enyl acetate gave ne...

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Bibliographic Details
Published in:Journal of organic chemistry 1998-08, Vol.63 (16), p.5533-5540
Main Authors: Koning, B, Meetsma, A, Kellogg, R. M
Format: Article
Language:English
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Summary:Pyridine thiols and dithiols have been synthesized by base-induced addition of 2,6-lutidine to thiofenchone. These thiols were converted to their thioether derivatives by alkylation. Application of these compounds in palladium-catalyzed allylic substitution on 1,3-diphenylprop-2-enyl acetate gave nearly absolute enantiomeric excess (98%) and high chemical yield (96%). Isolation of a palladium allylic intermediate gave insight in the origin of chiral recognition for these systems.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo9806299