Overriding ortho-para selectivity via a traceless directing group relay strategy: the meta-selective arylation of phenols

J Am Chem Soc. 2014 Mar 19;136(11):4109-12. doi: 10.1021/ja500457s. Epub 2014 Mar 11.

Abstract

The direct functionalization of phenols at the ortho and para position is generally facilitated by the electron-donating nature of the hydroxyl group. Accessing meta-functionalized phenols from the parent phenols, on the other hand, generally requires lengthy synthetic sequences. Here, we report the first methodology for the one-pot direct meta-selective arylation of phenols. This methodology is based on a traceless directing group relay strategy. In this process carbon dioxide is used as a transient directing group which facilitates a palladium catalyzed arylation meta to the phenol hydroxyl group with iodoarenes. This transformation proceeds with complete meta-selectivity and is compatible with a variety of functional groups both in the phenol and in the iodoarene coupling partner.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Carbon Dioxide / chemistry
  • Catalysis
  • Molecular Structure
  • Palladium / chemistry
  • Phenols / chemistry*
  • Stereoisomerism

Substances

  • Phenols
  • Carbon Dioxide
  • Palladium