Polyoxotungstate photoinduced alkylation of electrophilic alkenes by cycloalkanes.
Alkyl radical obtained by irradiation of tetrabutylammonium decatungstate in acetonitrile in the presence of cycloalkanes (C5H10, C6H12, C7H14) are efficiently trapped by electrophilic alkenes (acrylonitrile, isopropylydenmalonitrile, isopropylydencyanoacetate) to give the corresponding alkylated aliphatic nitriles. The reaction can be carried out up to complete conversion of the alkene with reasonable (in most cases 60-65 %) yields. Addition of the radicals to the alkene is followed by electron transfer from reduced decatungstate regenerating the sensitizer (turn over number up to 60). Steady-state measurements, EPR evidence, deuteration experiments and attempted intramolecular trapping of the adduct radical support the mechanistic proposal.
Dondi
Daniele
D
Department of Organic Chemistry, University of Pavia, via Taramelli 10, 27100 Pavia, Italy.
Fagnoni
Maurizio
M
Molinari
Alessandra
A
Maldotti
Andrea
A
Albini
Angelo
A