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Synthesis 1996; 1996(10): 1232-1238
DOI: 10.1055/s-1996-4355
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Insertion of α-Phosphorylcarbene Moiety into S-S and Se-Se Bonds: Synthesis of Dithio- and Diselenoacetals of Formylphosphonates

M. Mikołajczyk* , M. Mikina, P. P. Graczyk, P. Bałczewski
  • *Center of Molecular and Macromolecular Studies, Polish Academy of Sciences, Department of Organic Sulfur Compounds, P-90-363 Łódź, Sienkiewicza 112, Poland, Fax +48(42)847126
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Publication Date:
31 December 2000 (online)

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Reaction between diazomethanephosphonates and disulfides or diselenides catalyzed by boron trifluoride - diethyl ether complex leads to insertion of the (RO)2P(O)-CH(:) moiety into S-S and Se-Se bonds, respectively. The proposed method makes it possible to synthesize 2-phosphoryl-substituted 1,3-diselenanes, not available by other means. The yield depends on the reaction conditions. Stereoselectivity of insertion into cyclic systems is discussed. Reactions catalyzed by rhodium(II) acetate or anhydrous copper(II) sulfate afford the relevant sulfides, (RO)2P(O)-CH2SR. The possible ionic and free radical mechanistic pathways are presented.

insertion - dithioacetals - diselenoacetals - formylphosphonates - 1,3-diselenanes