METHOXY-(2-TRIMETHYLSILYL)ETHOXYCARBENE - REACTIONS WITH MICHAEL ACCEPTORS, WITH HYDROXYLIC COMPOUNDS, AND WITH MISCELLANEOUS FUNCTIONAL-GROUPS

Methoxy-(2-trimethylsilyl)ethoxycarbene reacts with two equivalents of dimethyl acetylene dicarboxylate, methyl propiolate, phenyl acetylene , or phenyl isocyanate without rearrangement of the carbene group. N-P henylmaleimide captures the carbene with 1:1-stoichiometry. The struct ure of the product implies that a migration of the trimethylsilylethyl group from oxygen to carbon accompanies that reaction. A mechanism fo r that complex rearrangement is proposed. Phenol and tert-butyl alcoho l afford the orthoformates expected from overall insertion of the carb ene into the OH bond.