Na₂S₂O₄-Promoted Radical Addition Reaction of Perfluoroalkyl Iodides with Allenes and the Pd(0)-Catalyzed Stereoselective Sonogashira Coupling Reaction of Addition Products with Propargyl Alcohol

Abstract

A Na₂S₂O₄-promoted radical addition reaction of per­fluoroalkyl iodides with allenes affording 1-perfluoroalkyl-2-alken-2-yl iodides 3 in 52-69% yields has been developed. Kinetic re­solution of the Z/E mixture via the Pd(0)-catalyzed Sonogashira coupling reaction was applied to prepare pure vinylic iodides (Z)-3 and the related coupling products (E)-4 up to 98:2 E/Z ratio.

Key words

perfluoroalkyl iodides - allenes - radical addition - propargyl alcohol - Sonogashira coupling

References and Notes

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11

Typical Procedure. The reaction of 1a (258.8 mg, 1.99 mmol), IC₄F₉ (2b, 1.0482 g, 3.03 mmol), Na₂S₂O₄ (523.6 mg, 3.01 mmol), and NaHCO₃ (253.4 mg, 3.02 mmol) in 16 mL of mixed solvent of 1,4-dioxane and H₂O (3:1) afforded 612.7 mg (65%) of 3b. ¹H NMR (400 MHz, CDCl₃): δ = 7.37-7.28 (m, 2 H), 7.28-7.20 (m, 2 H), 7.20-7.14 (m, 1 H), 6.84 (E isomer, t, J = 7.6 Hz, 0.36 H), 6.04 (Z isomer, t, J = 6.6 Hz, 0.64 H), 3.61-3.37 (m, 4 H). The E/Z mixture was subjected to the next step without further characterization.
Then the reaction of 3b (118.7 mg, 0.25 mmol, E/Z = 1:1.78), propargyl alcohol (8.5 mg, 0.15 mmol), Pd(PPh₃)₂Cl₂ (6.2 mg, 8.84 × 10^-3 mmol, 3.5 mol%), CuI (1.8 mg, 9.47 × 10^-3 mmol, 3.8 mol%), and Et₂NH (11.0 mg, 0.15 mmol) in 0.5 mL of MeCN afforded 50.9 mg (43%) of (Z)-3b, 4.0 mg (4%) of (Z)-4b, and 33.9 mg (34%) of (E)-4b.