Organothio sulfonyl carbenes 3 have been generated via ylid thermolysis or via a-elimination starting from a-chloro a-organothio sulfones and their derivatives. They have been captured by suitable nucleophilic trapping reagents (diazomethane, enol ethers, and others). Their nucleophilic carbenoid precursors could be trapped by an electrophilic olefin (ketene dithioacetal S,S-dioxides as Michael acceptors). Stable carbene Z-dimers could be obtained under various conditions. Bromine catalyzed isomerization to E-isomers proved to be reversible
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