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Base-Mediated Stereospecific Synthesis of Aryloxy and Amino Substituted Ethyl Acrylates

Kabir, M. Shahjahan, Namjoshi, Ojas A., Verma, Ranjit, Lorenz, Michael, Phani Babu Tiruveedhula, V. V. N., Monte, Aaron, Bertz, Steven H., Schwabacher, Alan W., Cook, James M.
Journal of organic chemistry 2012 v.77 no.1 pp. 300-310
Lewis bases, acrylates, chemical structure, cross-coupling reactions, heterocyclic nitrogen compounds, industry, organic chemistry, phenols, polymers, screening, stereoselectivity
The stereospecific synthesis of aryloxy and amino substituted E- and Z-ethyl-3-acrylates is of interest because of their potential in the polymer industry and in medicinal chemistry. During work on a copper-catalyzed cross-coupling reaction of ethyl (E)- and (Z)-3-iodoacrylates with phenols and N-heterocycles, we discovered a very simple (nonmetallic) method for the stereospecific synthesis of aryloxy and amino substituted acrylates. To study this long-standing problem on the stereoselectivity of aryloxy and amino substituted acrylates, a series of O- and N-substituted nucleophiles was allowed to react with ethyl (E)- and (Z)-3-iodoacrylates. Screening of different bases indicated that DABCO (1,4-diazabicyclo[2.2.2]octane) afforded successful conversion of ethyl (E)- and (Z)-3-iodoacrylates into aryloxy and amino substituted ethyl acrylates in a stereospecific manner. Herein are the details of this DABCO-mediated stereospecific synthesis of aryloxy and amino substituted E- or Z-acrylates.