Phosphonylated thiocarbonyl ylides from the reaction of aromatic thioketones with diethyl diazomethylphosphonates |
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Authors: | Stanislaw Lesniak Grzegorz Mloston Katarzyna Urbaniak Anthony Linden |
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Institution: | a Department of Organic and Applied Chemistry, University of ?ód?, Narutowicza 68, PL-90-136 ?ód?, Poland b Institute of Organic Chemistry, University of Zürich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland |
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Abstract: | The reaction of diazomethylphosphonates with aromatic thioketones at −65 °C to room temperature yields 2,5-dihydro-1,3,4-thiadiazole-2-phosphonates, which eliminates N2 to give phosphonylated thiocarbonyl ylides as reactive intermediates. These sulfur-centered 1,3-dipoles undergo typical reactions of thiocarbonyl ylides, i.e., 1,3-dipolar cycloadditions, cyclodimerization, and electrocyclic ring closure, depending on the involved thioketone and, therefore, on the reaction conditions. In the case of the most reactive thiofluorenone, the phsophonylated thiocarbonyl methanide can be intercepted with thiobenzophenone, a phosphonodithioformate, and tetracyanoethylene. In the absence of such reactive dipolarophiles, cyclodimerization occurs to give the corresponding 1,4-dithiane. |
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Keywords: | Diazo compounds Thioketones Thiocarbonyl ylides [2+3] Cycloadditions Cyclodimerization X-ray crystallography |
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