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Investigation of Silver-Catalyzed Propargylation Reactions and Nickel-Catalyzed Cross-Electrophile Couplings

  • Author(s): Endean, Thomas
  • Advisor(s): Jarvo, Elizabeth R
  • et al.

Metal-catalyzed reactions often allow access to reactivity that would be otherwise unavailable to researchers using more conventional synthetic methods. The Jarvo lab has worked to develop both stereoselective and stereospecific metal-catalyzed reactions that proceed with high stereochemical fidelity to produce synthetically useful products.

In Chapter 1 the enantioselective silver-catalyzed propargylation of N-sulfonylketimines is described. This reaction proceeds in high yield and excellent enantiomeric ratio and is compatible with a wide variety of diaryl and aryl-alkylketimines. The synthetic transformation of one of the homopropargylic products via Sonogashira cross-coupling proceeds with high stereochemical fidelity.

In Chapter 2 work towards a deeper understanding of the mechanism of a previously disclosed stereospecific nickel-catalyzed cross-electrophile coupling of 2-aryl-4-chlorotetrahydropyrans to form cyclopropanes is described. Experiments were performed to determine the overall rate law of the reaction as well as the kinetic order of each reagent participating in the rate-determining step of the reaction.

In Chapter 3 work towards a new stereospecific nickel-catalyzed cross-electrophile coupling is described. Utilizing a strained 2-aryl-oxetane scaffold with a pendant chloride the stereospecific cross-electrophile coupling to form cyclopropanes.

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