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DOI: 10.1055/s-0030-1258395
Synthesis and Reactivity of Divinylselenium Dichlorides and Dibromides
Publication History
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.
Key words
electrophilic additions - alkynes - alcohols - selenium - halides
- 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: 1 - 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
References
Commercially available.