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Silylcupration of Conjugated Alkynes and Copper-Hydride Reductions of Morita-Baylis-Hillman Adducts

  • Author(s): Peterson, Carl August
  • Advisor(s): Lipshutz, Bruce H
  • et al.
Abstract

There currently exists a need for more extensive mild and greener bond forming reactions that allow for construction of sophisticated carbon frameworks. Vinylsilanes have proven themselves to be valuable intermediates in organic synthesis. Traditionally, these educts have been difficult to access requiring stoichiometric metals which often precudes their use on scale. Herein, we investigated the use of Suginome’s reagent, PhMe2SiBpin, in a commercially available surfactant TPGS-750-M to afford isomerically pure (E)-β-silyl-substituted carbonyl derivatives by way of a copper catalyzed silylcupration in water at room temperature.

Copper hydride has seen extensive use as both an asymmetric and achiral source of hydride for many decades. We were interested in investigating copper hydride’s application toward Morita-Baylis-Hillman adducts given their possession of multiple electrophilic sites. We discovered that CuH could be used for tandem reductions of racemic MBH ketones lacking defined olefin geometry into valuable chiral allylic alcohol derivatives with defined stereochemistry.

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