Pd(II)-catalyzed hydroxyl-directed C-H olefination enabled by monoprotected amino acid ligands

Academic Article
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related to degree

  • Engle, Keary M., Ph.D. in Chemistry, Scripps Research 2008 - 2013
  • Wang, Donghui, Ph.D., Scripps Research , transferred from Brandeis Univeristy 2007 - 2010

publication date

  • April 2010

abstract

  • A novel Pd(II)-catalyzed ortho-C-H olefination protocol has been developed using spatially remote, unprotected tertiary, secondary, and primary alcohols as the directing groups. Mono-N-protected amino acid ligands were found to promote the reaction, and an array of olefin coupling partners could be used. When electron-deficient alkenes were used, the resulting olefinated intermediates underwent subsequent Pd(II)-catalyzed oxidative intramolecular cyclization to give the corresponding pyran products, which could be converted into ortho-alkylated alcohols under hydrogenolysis conditions. The mechanistic details of the oxidative cyclization step are discussed and situated in the context of the overall catalytic cycle.