An Efficient Electrochemical Method for the Paired Synthesis of Carbonyl Compounds and Homoallylic Alcohols in a Simple Home-Made Cell

Abstract

An efficient electrochemical synthesis of carbonyl compounds and homoallylic alcohols was developed in excellent yields using a simple home-made cell. The catalytic redox behavior of the electrode surface and the reaction mechanism was investigated by cyclic voltammetry (CV).

electrochemistry - paired synthesis - carbonyl compounds - homoallylic alcohols - home-made cell

References and Notes

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For details see the experimental section in the Supporting Information.

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Representative Procedure for 1-Phenylbut-3-en-1-ol and Benzaldehyde
A divided cell with salt bridge of KNO₃ was equipped with a graphite electrode (dia. 3.0 mm) as anode and a graphite electrode (dia. 3.0 mm vs. SCE) as cathode (Figure S₁ in Supporting Information). To a solution of KNO₃ (5 mL, 0.4 M) in the anodic compartment, benzyl alcohol (5 mmol) was added. In the cathodic compartment, a solution of allyl bromide (7.5 mmol) was added into 0.2 M SnCl₂ (5 mL)
and KNO₃ (0.4 M). The electrolytes were stirred and electrolyzed at constant potential of 0.6 V until the alcohols were transformed. The produced aldehyde was transferred to cathodic chamber by simple phase separation. Meanwhile, the same benzyl alcohol (5 mmol) was added in anodic chamber. The electrolytes were stirred and electrolyzed at constant potential of 0.6 V for 4-5 h. Meanwhile, the electrolytes were also electrolyzed at a constant current of
20 mA (14 h, 2 F/mol of current was consumed). Considering the period of reaction, we chose the potentiostatic method to carry out this reaction instead of galvanostatic method. Then the allylation product in cathode compartment was extracted with Et₂O (3 × 10 mL), washed with H₂O and dried over anhyd Na₂SO₄, respectively. The solvents were removed under reduced pressure, and the residues were purified by flash column chromatography. The produced aldehyde in the anodic compartment was separated by a phase separation and was added to the cathodic compartment for the next cycle.