Alkoxycarbonyl carbenes rearrangement

As stated above, an alkoxycarbonyl(disilanyl)carbene rearranges to an acylsilene, but not to a silylketene (Scheme 5). For diazoacetate 62, the result of a matrix-isolation experiment (Table 3) can also be reproduced when the nitrogen extrusion is induced by vacuum pyrolysis at 360 °C, by thermolysis of the neat compound at 180 °C or by photolysis in... 

Alkoxycarbonyl-l-silacyclobutanes, the starting materials for thermal rearrangements, can be accessed via a novel intramolecular 1,4-insertion of a carbene into the C-H bond of an Si-f-Bu group. 

---