Chemoselective Transesterification of Methyl (Meth)acrylates Catalyzed by Sodium(I) or Magnesium(II) Aryloxides

A highly chemoselective transesterification of methyl (meth)acrylates catalyzed by sterically demanding 2,6-di-tert-butyl-4-methylphenol-derived NaOAr or Mg(OAr)(2) was developed. The desired transesterification proceeded without the undesired Michael additions under mild reaction conditions at 25 degrees C, and various primary and secondary alcohols, diols, triol, and tetraol on a scale of up to 10 mmol could provide the corresponding functionalized acrylates in high yields. Transition states were proposed based on monomeric and dimeric active species, and computational density functional theory calculations strongly supported high chemoselectivity to minimize undesired Michael additions.

Automated summary

A highly chemoselective transesterification catalyzed by NaOAr or Mg(OAr)2 was developed, allowing for the production of functionalized acrylates without undesired Michael additions under mild reaction conditions. Computational density functional theory calculations supported the high chemoselectivity of this reaction.