WOLFF RAERRANGEMENT OF (1-DIAZO-2-OXOALKYL) SILANES

Article abstract of DOI:10.1016/S0040-4020(01)89498-9

Photochemical decomposition of (1-diazo-2-oxoalkyl) silanes 6a-l results in Wolff rearrangement yielding silyl ketenes 8a-l.From (1-diazo-3,3-dimethyl-2-oxobutyl) silanes 6c-f, 2-silyl-cyclobutanones 9c-f are formed as by-products, arising from intramolecular C/H insertion of the acyl carbene intermediate.Irradiation of diazo-triisopropylsilyl-acetamide 6m yields only β-lactam 16 and γ-lactam 17.Wolff rearrangement also takes place on copper triflate catalyzed decomposition of 6a,c,l, whereas the 1-oxa-2-sila-4-cyclopentene 19 is obtained from 6f, probably as the result of SiC/H insertion of a copper carbene intermediate.