@article{β-Functionalization:2255,
      recid = {2255},
      author = {Wang, Chengpeng},
      title = {Direct β-Functionalization of Ketones via  Palladium-Catalyzed Redox Cascade},
      publisher = {University of Chicago},
      school = {Ph.D.},
      address = {2020-06},
      pages = {477},
      abstract = {Based on versatile catalytic α,β-desaturation methods,  strategies that directly functionalize carbonyl compounds  at their less reactive β positions have emerged over the  past decade. Among the established methods, the redox  cascade strategy provides a distinct β-functionalization  approach in a step-economical and redox-neutral manner. It  is capitalized on reusing the Pd(0) species generated after  α,β-desaturation in a subsequent carbon halogen bond  activation, in which the electrophile serves as both the  oxidant and the source for the β substituent, thus  rendering an overall redox-neutral process. A direct  β-alkenylation of simple ketones is disclosed via  Pd-catalyzed redox cascade using readily available alkenyl  bromides as the functionalization reagents. A wide range of  sensitive functional groups are tolerated due to the mild  reaction conditions, and the alkenylated ketone products  can be diversely derivatized with various alkene  transformations. In addition, coupling of ketones and  aldehydes with simple alkyl bromides enables a direct  β-alkylation approach, which has found synthetic  applications in the synthesis of drug candidates. A copper  cocatalyst is essential for enhanced efficiency through  stabilizing radical intermediates and suppressing  overoxidation. Finally, a formal addition of β-C-H bonds of  ketones to alkynes is developed as a novel atom-economical  approach for β-functionalization. Systematic mechanistic  studies reveal a unique desaturation-mediated chain-like  mechanism which features an intermolecular β-hydrogen  transfer process.},
      url = {http://knowledge.uchicago.edu/record/2255},
      doi = {https://doi.org/10.6082/uchicago.2255},
}