Efficient Syntheses of (Thio)phosphonylated Isobenzofurans by Tandem Nucleophilic Addition and Regioselective 5‐exo‐dig Addition to Carbon‐Carbon Triple Bond: Cooperative Effect to 1,8‐Diazabicyclo[5.4.0]undec‐7‐ene (DBU)

The tandem nucleophilic addition-cyclization reaction of o-alkynylbenzaldehydes or o-alkynylacetophenones 2 with dialkyl phosphites or dialkyl phosphonothioates 1 took place very smoothly in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in THF at room temperature. In all cases, the reaction proceeded in a regioselective manner leading to the 5-exo-dig products 3 in excellent yields. The phenomenon of a 1,5-sigmatropic hydrogen shift or a 1,5-sigmatropic methyl shift was observed in this reaction depending on the different substituent groups such as R 3 in the o-alkynylbenzaldehyde or oalkynylacetophenone 2 substrates.

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