Reaction of anions with activated olefins in the gas phase. A flowing afterglow-selected ion flow tube study

Article abstract of DOI:10.1021/ja00181a003

Reactions of anions with acrylonitrile, acrolein, methyl vinyl ketone, and methyl acrylate at room temperature under SIFT conditions are described. Stabilized carbanions such as benzyl anion, cyanomethyl anion, cyclohexadienide, acetone enolate, and nitromethyl anion add to activated carbon-carbon double bonds in a process that is competitive with other modes of reaction. With acrylonitrile and methyl acrylate, addition is in a 1,4 or Michael fashion, while with acrolein and methyl vinyl ketone, 1,2 addition competes with 1,4 addition. Hydroxide, methoxide, fluoride, and cyanide do not add to activated olefins by either mode (see Tables I-IV). A mechanism is proposed for hydride transfer from cyclohexadienide to activated olefins.