Synthesis and Reactivity of Divinylselenium Dichlorides and Dibromides

Abstract

Regio- and stereospecific electrophilic addition reactions of selenium tetrachloride and selenium tetrabromide to propargyl alcohols are reported. (Z,Z)-Bis(β-chlorovinyl)selenium dichlorides were isolated in high yields, and their reactivity was dependent on their substitution pattern. Products derived from unsubstituted, α-methyl-, or α,α-dimethylpropargyl alcohols readily underwent transfer of chlorine atoms to one of the two double bonds. (Z,Z)-Bis(β-chlorovinyl)selenium dichlorides derived from γ-phenyl- or γ-isopropenylpropargyl alcohols underwent cyclization to form benzoselenophene derivatives; this was accompanied by the formation of the corresponding dichloro-substituted allylic alcohols. In contrast, selenium tetrachloride reacts with γ-phenylpropargyl alcohol exclusively as a chlorinating agent, giving (3-chloroprop-1-yn-1-yl)benzene quantitatively. Products of regio- and stereospecific electrophilic addition of selenium tetrabromide are also described. Reaction mechanisms are proposed.

Key words

electrophilic additions - alkynes - alcohols - selenium - halides

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