title: Base-mediated stereospecific synthesis of aryloxy and amino substituted ethyl acrylates.
abstract: 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.
authors.affiliation: Department of Chemistry and Biochemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, United States. capncook@uwm.edu
authors.forename: M Shahjahan
authors.initials: MS
authors.lastname: Kabir
authors.forename: Ojas A
authors.initials: OA
authors.lastname: Namjoshi
authors.forename: Ranjit
authors.initials: R
authors.lastname: Verma
authors.forename: Michael
authors.initials: M
authors.lastname: Lorenz
authors.forename: V V N Phani Babu
authors.initials: VV
authors.lastname: Tiruveedhula
authors.forename: Aaron
authors.initials: A
authors.lastname: Monte
authors.forename: Steven H
authors.initials: SH
authors.lastname: Bertz
authors.forename: Alan W
authors.initials: AW
authors.lastname: Schwabacher
authors.forename: James M
authors.initials: JM
authors.lastname: Cook
mesh_terms: D000179:Acrylates / Q000138:chemical synthesis* / Q000737:chemistry; D000586:Amination; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D003432:Cross-Linking Reagents / Q000737:chemistry*; D015394:Molecular Structure; D010647:Phenyl Ethers / Q000138:chemical synthesis* / Q000737:chemistry; D011108:Polymers / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000179:Acrylates; D003432:Cross-Linking Reagents; D010647:Phenyl Ethers; D011108:Polymers; C040833:ethyl acrylate; D003300:Copper
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