title: Studies on elimination pathways of β-halovinyl ketones leading to allenyl and propargyl ketones and furans under the action of mild bases.
abstract: The elimination pathway of stereochemically defined β-halovinyl ketones has been investigated using a mild base, NEt(3), leading to the formation of allenyl ketones and propargyl ketones. A preferential α-vinyl enolization of (E)-β-chlorovinyl ketones has been observed where a nonplanar s-cis conformation is proposed as a dominant conformation as opposed to a planar s-cis conformation of (Z)-β-chlorovinyl ketones. Other eliminative pathways, such as concerted syn- and anti-E2 as well as γ-deprotonation, are excluded on the basis of the deuterium isotope studies. The synthetic utility of the elimination reaction of β-chlorovinyl ketones was further demonstrated for a one-pot synthesis of 2,5-disubstituted furans in the presence of 1 mol % CuCl.
authors.affiliation: Department of Chemistry and Chemical Biology, Indiana University-Purdue University Indianapolis, Indianapolis, Indiana 46202, USA.
authors.forename: Hun Young
authors.initials: HY
authors.lastname: Kim
authors.forename: Jian-Yuan
authors.initials: JY
authors.lastname: Li
authors.forename: Kyungsoo
authors.initials: K
authors.lastname: Oh
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000480:Alkynes / Q000737:chemistry*; D005663:Furans / Q000737:chemistry*; D054879:Halogenation; D006863:Hydrogen-Ion Concentration; D007659:Ketones / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation
chemical_list: D000475:Alkenes; D000480:Alkynes; D005663:Furans; D007659:Ketones