Silver-Catalyzed Allenylation and Enantioselective Propargylation Reactions of Ketones


  • This work was supported by an NSF CAREER Award (CHE-0847273), Vertex Graduate Fellowship, UCI Regents Dissertation Fellowship (B.L.K.), and UROP, NSF-REU, and Allergan Undergraduate Fellowships (N.I.). Charlotte A. Osborne is acknowledged for Table 2, entry 4. Chanel R. Easley is acknowledged for preliminary studies of related transformations. We thank Solvias and Frontier Scientific for donations of chemicals. Dr. John Greaves is acknowledged for mass spectrometry data.


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More than a silver lining: Certain silver complexes are capable of selective catalysis of either allenylation or asymmetric propargylation reactions of ketones. Ligand-free conditions lead to allenyl alcohols as the major product, whereas ligation with Walphos-8 gives enantioenriched homopropargyl alcohols. This method can be applied to reactions of prochiral diarylketones to provide optically enriched tertiary diaryl alcohols.