Elektrophile alkylierung von dimethylphosphono- und diphenylphosphinyldiazomethan mit enaminen

λ5-Phosphorus-Containing α-Diazo Compounds: A Valuable Tool for Accessing Phosphorus-Functionalized Molecules

“…In the ' s Regitz's g oup pu lished so e pape s epo ti g the su stitutio of the α-hydrogen of dimethyl α-diazomethylphosphonate (5a) and diphenyl α-diazomethylphosphinoxide (2b) by electrophilic reagents. 66,67,68,33 Fu the o e, α-e z l-α-diazo eth lphospho ate de i ati es e e e e tl p epa ed i e good ield the ea tio of e z l o ides ith the a io of a, ge e ated i -situ f o BOR " he e . Ho e e , i the ase of e z l o ides ea i g ele t o -ithd a i g su stitue ts at the orthoo parapositio , it oge eli i atio o u ed fu ishi g the espe ti e st lphospho ates .…”

“…As far back as 1972, Regitz et al reported the reaction 1β9 of dimethyl diazomethylphosphonate (5a) and diphenyl diazomethylphosphinoxide (2a) with a seies of li α-dicarbonyl derivatives fu ishi g the o espo di g β-hydroxy-α-diazophosphono derivatives 316a-o (Scheme 142). 219,66,220 Under anhydrous acidic conditions the diazoaldols 316a-o gave the corresponding ring-enlarged products 317a-o through the intermediate carbocations. Decomposition of the diazoaldols 318a-g, prepared as described above, in the presence of ethereal hydrochloric acid, afforded the corresponding (2-hydroxyvinyl)diphenylphosphinoxides 320b-g, as a consequence of migration of the R group in the carbocation intermediates 319b-g (Scheme 144).…”

“…In the 1970s, Regitz’s group published some papers reporting the substitution of the α-hydrogen of dimethyl α-diazomethylphosphonate ( 5a ) and diphenyl α-diazomethylphosphinoxide ( 2b ) by electrophilic reagents. ,− α-Halo- and α-alkylated PCDCs were thus prepared via silver or mercury diazo intermediates, as summarized in Table .…”

“…As far back as 1972, Regitz et al reported the reaction of dimethyl diazomethylphosphonate ( 5a ) or diphenyl diazomethylphosphinoxide ( 2a ) with a series of cyclic α-dicarbonyl derivatives, furnishing the corresponding β-hydroxy-α-diazophosphono derivatives 316a – o (Scheme ). ,, Under anhydrous acidic conditions, the diazoaldols 316a – o gave the corresponding ring-enlarged products 317a – o through the intermediate carbocations.…”