Palladium-Catalyzed Carbonylative Synthesis of Benzogerminones

Abstract

A novel and practical procedure for the synthesis of benzogerminones by carbonylative cyclization has been developed. With Pd(PPh₃)₄ as the catalyst and DABCO as the base, the desired benzogerminones were isolated in moderate to good yields with good functional group tolerance. To the best of our knowledge, this is the first procedure for benzogerminones synthesis.

Key words

palladium catalyst - carbonylation - cyclization - benzogerminone - heterocycle synthesis

• References and Notes

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• 11 General Procedure Under an open atmosphere, a 4 mL screw cap vial was charged with Pd(PPh₃)₄ (1 mol%), DABCO (0.3 mmol), alkyne (0.2 mmol), dibutyl(2-iodophenyl)germane (0.2 mmol), toluene (1 mL), and an oven-dried stirring bar. The vial was closed by a Teflon septum and a phenolic cap and connected to the atmosphere through a needle. Then the vial was fixed in an alloy plate and put into Paar 4560 series autoclave (300 mL). At room temperature, the autoclave is flushed with carbon monoxide for three times and 10 bar of carbon monoxide was charged. The autoclave was placed on a heating plate equipped with magnetic stirring and an aluminum block. The reaction was heated at 100 °C for 16 h. Afterwards, the autoclave was cooled to room temperature and the pressure carefully released. After removal of solvent under reduced pressure, pure product was obtained by column chromatography on silica gel (eluent: pentane/ethyl acetate, 20:1). Compound 3aa: eluting with n-heptane and ethyl acetate 30:1 (v/v), colorless oil, 61 mg, yield 77%. ¹H NMR (500 MHz, chloroform-d): δ = 8.28–8.25 (m, 1 H), 7.46–7.43 (m, 3 H), 7.32–7.22 (m, 7 H), 1.38–1.30 (m, 4 H), 1.26–1.21 (m, 4 H), 1.09 (dq, J = 10.1, 6.5 Hz, 4 H), 0.78 (t, J = 7.2 Hz, 6 H). ¹³C NMR (126 MHz, CDCl₃): δ = 188.15, 155.88, 145.35, 142.03, 141.77, 140.49, 133.23, 131.09, 130.02, 129.23, 128.68, 127.87, 127.61, 27.38, 26.05, 14.28, 13.64. HRMS (EI): m/z calcd for C₂₃H₂₈GeO [H]⁺: 391.1461; found: 391.1461.