1514677-79-2Relevant academic research and scientific papers
Cation control of diastereoselectivity in iridium-catalyzed allylic substitutions. formation of enantioenriched tertiary alcohols and thioethers by allylation of 5H-oxazol-4-ones and 5H-thiazol-4-ones
Chen, Wenyong,Hartwig, John F.
supporting information, p. 377 - 382 (2014/01/23)
We report highly diastereo- and enantioselective allylations of substituted 5H-oxazol-4-ones and 5H-thiazol-4-ones catalyzed by a metallacyclic iridium complex. Enantioselective Ir-catalyzed allylation of substituted 5H-oxazol-4-ones occurs with high diastereoselectivity by employing the corresponding zinc enolates; enantioselective Ir-catalyzed allylation of substituted 5H-thiazol-4-ones occurs with the corresponding magnesium enolates with high diastereoselectivity. The allylation of substituted 5H-oxazol-4-ones provides rapid access to enantioenriched tertiary α-hydroxy acid derivatives unavailable through Mo-catalyzed allylic substitution. The allylation of substituted 5H-thiazol-4-ones provides a novel method to synthesize enantioenriched tertiary thiols and thioethers. The observed cation effect implies a novel method to control the diastereoselectivity in Ir-catalyzed allylic substitution.
