Diethyl allylphosphonate

clear colorless liquid

Reactant for:

• Copolymerization of phosphonated allyl monomers and maleic anhydride
• Enantioselective synthesis of solamin type mono-THF acetogenins
• RCM reaction yielding oxaphospholene and oxaphosphinene heterocycles
• Synthesis of spongistatin 2 using Wittig coupling
• Stereoselective synthesis of pentacyclic furanosteroids
• Preparation of protected polyhydroxylated β -amino acid constitutents of microsclerodermins

To a stirred solution of diethyl allylphosphonate (582.5 mg, 3.0 mmol, 1.5 equiv) in dry THF (25 mL) was added NaH (60% dispersion in mineral oil, 120 mg, 3.0 mmol, 1.5 equiv) portion wise under nitrogen atmosphere at 0°C. After 15 min, aryl/alkyl aldehyde 14a–x, 14z (2.0 mmol) in dry THF was added to the reaction mixture and stirred at 0°C until the completion (monitored by TLC) of reaction. It was then quenched with saturated aq. NH4Cl and the solution was extracted with EtOAc (2×20 mL). The combined organic layers were dried (Na2SO4) and concentrated. The residue was purified by silica gel column chromatography using petroleum ether/EtOAc (9:1, common for all compounds unless specified) as eluent to afford (E)-1-aryl/alkylbutadienes 7a–x, 7z.
The CM reaction of 2 with dimethyl vinylphosphonate (3a) and diethyl allylphosphonate (3b) under a classic thermal condition with 3 mol % of H-G II at 40 °C.

Synthetic Communications, 22, p. 2219, 1992 DOI: 10.1080/00397919208019075
Synthesis, p. 563, 1986 DOI: 10.1055/s-1986-31704

reaction type: C-C Bond Formation

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