Wolff rearrangement of (1-diazo-2-oxoalkyl) silanes
作者:Ralf Brückmann、Klaus Schneider、Gerhard Maas
DOI:10.1016/s0040-4020(01)89498-9
日期:1989.1
(1-diazo-2-oxoalkyl) silanes 6a-1 results in Wolffrearrangement yielding silyl ketenes 8a-1. 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. Wolffrearrangement also takes place on copper triflate
Synthesis of 5-alkylidene-4,5-dihydro-3H-1,2,4(λ3)-diazaphospholes from α-silyl-α-diazoketones and phosphaalkenes
作者:Berthold Manz、Gerhard Maas
DOI:10.1016/0040-4020(96)00541-8
日期:1996.7
5-Alkylidene-4,5-dihydro-3H-1,2,4(λ3)-diazaphospholes (II) arise from a [3+2] cycloaddition reaction between various, differently substituted phosphaalkenes and 2-siloxy-1-diazoalkenes that are present to a minor extent in a thermal equilibrium with α-silyl-α-diazoketones. The cycloaddition products 4a-g,6a,b,e,f, and 8 are sufficiently thermally stable to be isolated. In other cases, silyl group migration