Diels–Alder reaction of 2-phosphaindolizines catalysed by organoaluminium reagent: theoretical and experimental results

Abstract

Theoretical calculations at the DFT (B3LYP/6-31+G**) level of the model Diels–Alder (DA) reactions of 1-methyl-3-(methoxycarbonyl)-2-phosphaindolizine with 1,3-butadiene in the presence of methylaluminium dichloride reveal that the co-ordination of organoaluminium reagent to the carbonyl oxygen increases the activation barrier compared to that for the uncomplexed 2-phosphaindolizine. On the other hand, co-ordination of the organoaluminium reagent to the σ2, λ3 P atom lowers the activation barrier by ∼6kcalmol−1. 1-Methyl-2-phosphaindolizines having an electron-withdrawing group at the 3-position only undergo DA reaction with 2,3-dimethylbutadiene in the presence of the ethylaluminium dichloride catalyst in methylene chloride at a low temperature to afford [2+4] cycloadducts. The formation of an intermediate having the ethylaluminium reagent co-ordinated to σ2, λ3 P atom has been detected by 31P NMR. The products have been characterized by 31P and 1H NMR studies.