First One Step Regioselective Acylation

  • Author: Li Grundl
  • Published: 05 August 2018
  • Copyright: Wiley-VCH Verlag GmbH & Co. KGaA
  • Source / Publisher: Journal of the American Chemical Society/ACS Publications
  • Associated Societies: American Chemical Society (ACS), USA
thumbnail image: First One Step Regioselective Acylation

The Friedel-Crafts acylation, an electrophilic aromatic substitution with electronic-controlled regioselectivity, is a commonly used method to synthesize aryl ketones. Although regioselective arene acylation using other approaches is possible, it usually requires multiple steps and precious-metal catalysts.


Christopher J. Douglas and colleagues, University of Minnesota—Twin Cities, Minneapolis, USA, have developed a new method for the sterically controlled regioselective acylation of arenes and heteroarenes (example product pictured). The team used phenyl salicylates as the acylation reagents, [Ir(cod)OMe]2 (cod = 1,5-cyclooctadiene) as a catalyst, and rac-2-(di-tert-butylphosphino)-1,1'-binaphthyl as a ligand. The reactions were performed in the respective arenes or heteroarenes, which were used in solvent quantities, at 170 °C.


The reaction tolerates a broad range of functional groups on the salicylate ester. Simple electron-rich arenes as substrates react particularly well under the conditions. The researchers suggest that the sterically controlled acylation is achieved via a concerted metalation–deprotonation C–H activation. The developed reaction offers substitution patterns previously inaccessible in a single step. The method's usefulness was demonstrated by a concise synthesis of the anticancer agent hydroxyphenstatin.


 

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