Schlosser, ManfredWei, Heng-xu2006-03-032006-03-032006-03-03199710.1016/S0040-4020(96)01075-7https://infoscience.epfl.ch/handle/20.500.14299/226946The elusive (E)-2-ethoxyvinyllithium can be readily generated in THF at -75 Deg from (E)-1-bromo-2-ethoxyethylene by halogen/metal exchange and subsequently trapped with electrophiles. Alkylation opens a convenient entry to (E)-configurated enethers. (E)-2-Ethoxyvinyllithium decomps. rapidly at -50 Deg whereas its (Z)-isomer, which lacks the possibility to eliminate LiOEt in a favorable antiperiplanar process, is stable under the same conditions. (E)-1,2-Diethoxyvinyllithium even sustains reflux temps. (.apprx.75 Deg). 2,2-Diethoxyvinyllithium and (Z)-1,2-diethoxyvinyllithium can be conserved at 0 Deg although this time loss of alcoholate can occur in the anti-mode. Obviously it matters whether the energy-rich ethoxyacetylene is formed as the elimination product or simple acetylene, as in the case of (E)-2-ethoxyvinyllithium. [on SciFinder (R)]Ethers Role: SPN (Synthetic preparation)PREP (Preparation) (ene; ethoxyvinyllithiums and diethoxyvinyllithiums for stereoselective prepn. of); Thermal decomposition (of ethoxyvinyllithiums and diethoxyvinyllithiums); Solvent effect (on thermal stabiliethoxyvinyllithium prepn stability alkylation; diethoxyvinyllithium prepn stability alkylation; thermal stability ethoxyvinyllithium diethoxyvinyllithium; stereoselective alkylation ethoxyvinyllithium diethoxyvinyllithium; enether stereoselective prepntext::journal::journal article::research article