Stereochemical Studies on the Nucleophilic Substitution in the Reaction of Allylic Phosphates with Organoaluminum Reagents

Article abstract of DOI:10.1246/bcsj.53.2357

The reaction of cis- or trans-5-isopropenyl-2-methyl-2-cyclohexenyl diethyl phosphate (1) with Me2AlX (X= OPh, SPh, NHPh) in hexane results in substitution of the -O-PO(OEt)2 group with X under predominant inversion.In contrast, treatment of cis- or trans-1 with trialkylaluminum produces predominantly the allyl-nonallyl coupling products of the same (thermodynamically more stable) configuration.Similar alkylation of endo- and exo-2-acetoxynorcarane gave endo-2-methylnorcarane, exclusively.