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Synthesis 2011(4): 577-584  
DOI: 10.1055/s-0030-1258395
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis and Reactivity of Divinylselenium Dichlorides and Dibromides

Samuel Braverman*, Tatiana Pechenick-Azizi, Hugo E. Gottlieb, Milon Sprecher
Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel
Fax: +972(3)7384053; e-Mail: bravers@mail.biu.ac.il;
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Publication History

Received 15 November 2010
Publication Date:
11 January 2011 (online)

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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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