Double α-Addition Reaction of ortho-Hydroxyacetophenones to Ethyl Propiolates Mediated by Ph₃P: Synthesis of Functionalized 1,4-Pentadienes

Abstract

A new way of synthesizing functionalized 1,4-pentadienes by double α-addition reaction of ortho-hydroxyaceto­phenones to ethyl propiolate mediated by Ph₃P in moderate yields is described. On the other hand, other ortho-hydroxyphenyl ketones resulted in the single α-addition products in moderate to good yields.

α-addition - functionalized 1,4-pentadienes - Ph₃P - ortho-acylphenols - ethyl propiolates

References and Notes

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General Reaction Procedure
To a solution of ortho-acylphenols (0.6 mmol) with terminal alkynoates (0.6 mmol) in dry CH₂Cl₂ (2 mL) was added Ph₃P (79 mg, 0.3 mmol), and the resulting mixture was stirred at r.t. for 16 h. The solvent was removed in vacuo, and the residue was purified by column chromatography on silica gel (PE-EtOAc = 20:1) to give the desired product.