Reactivity Pattern of Bis(propargyloxy) Disulfides: Tandem Rearrangements and Cyclizations

 

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Abstract

Thirty-five substituted bis(propargyloxy) disulfides were successfully prepared in good to excellent yields, and their reactivity was found to be strongly dependent on the substitution pattern of the reactant. Inter alia they undergo surprising tandem sigmatropic rearrangements and cycloadditions. Three heretofore unknown product types were isolated and fully characterized: 6,7-dithiabicyclo[3.1.1]heptan-2-one 6-oxide derivatives, two isomeric 1,2-dithiete 1,1-dioxides (α,β-unsaturated four-membered cyclic thiosulfonates) from bis(propargyloxy) disulfides with α- or γ-alkyl-substituted propargyl groups, and two isomeric 2-oxa-5,7-dithiabicyclo[2.2.1]heptane 5-oxides from bis(propargyloxy) disulfides with α-tert-butyl- or α,α-dialkyl-substituted propargyl groups.

References

• 1 Lengfeld F. Ber. Dtsch. Chem. Ges.  1895,  28:  449 
  CrossrefGoogle Scholar
• 2a Borghi R. Lunazzi L. Placuccu G. Cerioni G. Plumitallo A. J. Org. Chem.  1996,  61:  3327 
  Google Scholar
• 2b Borghi R. Lunazzi L. Placuccu G. Cerioni G. Plumitallo A.
  J. Org. Chem.  1997,  62:  4924 
  Google Scholar
• 2c Cerioni G. Plumitallo A. Magn. Reson. Chem.  1998,  36:  461 
  Google Scholar
• 3a Tardif SL. Williams CR. Harpp DN. J. Am. Chem. Soc.  1997,  119:  12685 
  Google Scholar
• 3b Derbesy G. Harpp DN.
  J. Org. Chem.  1996,  61:  991 
  Google Scholar
• 3c Tardif SL. Harpp DN. J. Org. Chem.  2000,  65:  4791 
  Google Scholar
• 3d Tardif SL. Williams CR. Harpp DN. J. Am. Chem. Soc.  1995,  117:  9067 
  Google Scholar
• 3e Priefer R. Farrell PG. Harpp DN. Tetrahedron Lett.  2002,  43:  8781 
  Google Scholar
• 4a Steudel R. Miaskiewicz K. J. Chem. Soc., Dalton Trans.  1991,  2395 
  Google Scholar
• 4b Steudel R. Schmidt H. Baumeister E. Oberhammer H. Koritsanszky T. J. Phys. Chem.  1995,  99:  8987 
  Google Scholar
• 4c Koritsanszky T. Buschmann J. Schmidt H. Steudel R. J. Phys. Chem.  1994,  98:  5416 
  Google Scholar
• 5a Zysman-Colman E. Harpp DN. Heteroat. Chem.  2007,  18:  449 
  Google Scholar
• 5b Eghbali N. Bohle DS. Harpp DN.
  J. Org. Chem.  2006,  71:  6659 
  Google Scholar
• 5c Zysman-Colman E. Nevins N. Eghbali N. Snyder JP. Harpp DN. J. Am. Chem. Soc.  2006,  128:  291 
  Google Scholar
• 5d Zysman-Colman E. Harpp DN. J. Org. Chem.  2005,  70:  5964 
  Google Scholar
• For a review, see:
• 5e Zysman-Colman E. Harpp DN. J. Sulfur Chem.  2004,  25:  155 
  Google Scholar
• 6 Thompson QE. Crutchfield MM. Dietrich MW. Pierron E. J. Org. Chem.  1965,  30:  2692 
  CrossrefGoogle Scholar
• 7a Pechenick T. Ph. D. Thesis   Bar-Ilan University; Israel: 2004. 
  Google Scholar
• 7b Braverman S. Pechenick T. Tetrahedron Lett.  2002,  43:  499 
  Google Scholar
• 7c Braverman S. Pechenick T. Gottlieb HE. Tetrahedron Lett.  2003,  44:  777 
  Google Scholar
• 7d Braverman S. Pechenick T. Gottlieb HE. Sprecher M. J. Am. Chem. Soc.  2003,  125:  14290 
  Google Scholar
• 8a Freeman F. Chem. Rev.  1984,  84:  117 
  Google Scholar
• 8b Lacombe SM. Rev. Heteroat. Chem.  1999,  21:  1 
  Google Scholar
• 10a Block E. Angew. Chem. Int. Ed. Engl.  1992,  31:  1135 
  Google Scholar
• 10b Block E. Thiruvazhi M. Toscano PJ. Bayer T. Grisoni S. Zhao SH. J. Am. Chem. Soc.  1996,  118:  2790 
  Google Scholar
• 10c Block E. Bayer T. Naganathan S. Zhao SH. J. Am. Chem. Soc.  1996,  118:  2799 
  Google Scholar
• 11a Block E. Bazzi AA. Revelle LK. J. Am. Chem. Soc.  1980,  102:  2490 
  Google Scholar
• 11b Baudin J.-B. Commenil M.-G. Julia SA. Wang Y. Bull. Soc. Chim. Fr.  1996,  133:  515 
  Google Scholar
• For a general review on sulfines, see:
• 11c Zwanenburg B. Recl. Trav. Chim. Pays-Bas  1982,  101:  1 
  Google Scholar
• 13a Amato JS. Karady S. Reamer RA. Schlegel HB. Springer JP. Weinstock LM. J. Am. Chem. Soc.  1982,  104:  1375 
  Google Scholar
• 13b Rayner DR. Gordon AJ. Mislow K.
  J. Am. Chem. Soc.  1968,  90:  4854 
  Google Scholar
• 13c Baechler RD. Andose JD. Stackhouse J. Mislow K. J. Am. Chem. Soc.  1972,  94:  8060 
  Google Scholar
• 13d Mock WL. J. Am. Chem. Soc.  1970,  92:  7610 
  Google Scholar
• 13e Toyota S. Rev. Heteroat. Chem.  1999,  21:  139 
  Google Scholar

Bis(propargyloxy) disulfide 9d did not undergo rearrangement. No rationale is proposed. After six hours in chloroform solution at room temperature, the compound decomposed to the corresponding propargylic alcohol 2d.

The stereochemistry of the two double bonds in these structures was established by NOESY experiments, which showed a strong interaction of the respective bridgehead hydrogen atoms with the nearby tert-butyl hydrogen atoms, but no interaction with the vinyl hydrogen atoms.

In the case of 9b, this reaction was repeated in anhydrous chloroform (dried over basic alumina) and found to be identical to the present one.

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