New Bridges in [2.2]Paracyclophanes: The Interaction of Chalcogenide Halides with Pseudo-Geminal Triple Bonds

Abstract

Novel heteroatom containing bridges have been introduced in [2.2]paracyclophanes by the interaction of chalcogenide halides with pseudo-geminal triple bonds. The anti-addition with Markovnikov orientation of selenium halides to 4,15-bisethynyl[2.2]paracyclophane leads to the corresponding E-adducts. The interaction of pseudo-geminally substituted bispropargylic alcohols with disulfur dichloride and sulfur dichloride leads to a mixture of cyclic ethers. These compounds are formed under mild acidic conditions provided by the organic ammonium chlorides or silica gel. The corresponding dipropargyloxy sulfides have been identified as reaction intermediates.

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Keywords:

• [2.2]Paracyclophanes
• selenium electrophiles
• sulfur electrophiles

Acknowledgments

This work was supported by CNCSIS–UEFISCSU, project number PNII–IDEI 2095/2008.