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: [email protected];
Further Information

Publication History

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

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.

    References

  • 1 Braverman S. Segev D. J. Am. Chem. Soc.  1974,  96:  1245 
  • 2 Braverman S. Pechenick T. Gottlieb HE. Sprecher M. J. Am. Chem. Soc.  2003,  125:  14290 
  • 3 Maaninen A. Chivers T. Parvez M. Pietikäinen J. Laitinen RS. Inorg. Chem.  1999,  38:  4093 
  • 4 Braverman S. Jana R. Cherkinsky M. Gottlieb HE. Sprecher M. Synlett  2007,  2663 
  • 5 Braverman S. Cherkinsky M. Jana R. Kalendar Yu. Sprecher M. J. Phys. Org. Chem.  2010,  23:  1114 
  • 6 Garratt DG. Ujjainwalla M. Schmid GH. J. Org. Chem.  1980,  45:  1206 
  • 7 Migalina YuV. Galla-Bobik SV. Khripak SM. Staninets VI. Khim. Geterotsikl. Soedin.  1982,  911 ; Chem. Abstr. 1982, 97, 162496
  • 8 Migalina YuV. Galla-Bobik SV. Ershova II. Staninets VI. Zh. Obshch. Khim.  1982,  52:  1559 ; Chem. Abstr. 1982, 97, 162292
  • 9 Engman L. J. Org. Chem.  1987,  52:  4086 
  • 10 Garratt DG. Schmid GH. Can. J. Chem.  1974,  52:  3599 
  • 11 Magnus PD. In Comprehensive Organic Chemistry   Vol. 3:  Barton DHR. Ollis WD. Pergamon; Oxford: 1979.  p.489 
  • 12a Riley RF. Flato J. Bengels D. J. Org. Chem.  1962,  27:  2651 
  • 12b Migalina YuV. Galla-Bobik SV. Lendel VG. Staninets VI. Khim. Geterotsikl. Soedin.  1981,  1283 ; Chem. Abstr. 1982, 96, 6522
  • 12c Minh TQ. Christiaens L. Renson M. Bull. Soc. Chim. Fr.  1974,  2239 
  • 12d Riley RF. Flato J. McIntyre P. J. Org. Chem.  1963,  28:  1138 
  • 13a Martynov AV. Ivanov AV. Amosova SV. Potapov VA. Russ. J. Org. Chem.  2006,  42:  1083 
  • 13b Potapov VA. Khuriganova OI. Musalov MV. Larina LI. Amosova SV. Russ. J. Gen. Chem.  2010,  80:  541 
  • 13c Potapov VA. Amosova SV. Belozerova OV. Albanov AI. Yarosh OG. Voronkov MG. Chem. Heterocycl. Compd. (N. Y., NY, U. S.)  2003,  39:  551 
  • 13d Amosova SV. Shagun VA. Martynov AV. Makhaeva NA. Larina LI. Lysenko KA. Voronkov MG. J. Organomet. Chem.  2007,  692:  3307 
  • 13e Amosova SV. Martynov AV. Mahaeva NA. Belozerova OV. Penzik MV. Albanov AI. Yarosh OG. Voronkov MG. J. Organomet. Chem.  2007,  692:  946 
  • 13f Amosova SV. Penzik MV. Martynov AV. Zhilitskaya LV. Voronkov MG. Russ. J. Gen. Chem.  2009,  79:  221 
  • 13g Amosova SV. Martynov AV. Mini-Rev. Org. Chem.  2010,  7:  23 
  • 13h Amosova SV. Penzik MV. Martynov AV. Makhaeva NA. Yarosh NO. Voronkov MG. J. Organomet. Chem.  2008,  693:  3346 
  • 14 Duddeck H. Prog. Nucl. Magn. Reson. Spectrosc.  1995,  27: 
  • 15 Lendel VG. Sani AY. Migalina Yu. Pak BI. Balog IM. Khim. Geterotsikl. Soed.  1989,  564 ; Chem. Abstr. 1990, 112, 77120
  • 17 Yamauchi T. Hattori K. Mizutaki S. Tamaki K. Uemura S. Bull. Chem. Soc. Jpn.  1986,  59:  3617 
  • 18a Toda F. Takahara Y. Bull. Chem. Soc. Jpn.  1976,  49:  2515 
  • 18b Toda F. Ohi M. J. Chem. Soc., Chem. Commun.  1975,  506 
16

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