Diastereoselective Ultrasonically Induced Zinc-copper Conjugate Addition to Chiral α,β-Unsaturated Carbonyl Systems in Aqueous Media

Abstract

The diastereoselective ultrasonically induced zinc-copper 1,4-addition of alkyl iodides to chiral α,β-unsaturated systems 1-3 in aqueous media is reported. The reaction of methylenedioxolanone 1 with a variety of alkyl iodides takes place in good yields and with high diastereomeric excess. The 1,4-addition to (Z)- and (E)-γ,δ-dioxolanyl-α,β-unsaturated esters 2 and 3 also proceeds with good yields: the Z-isomer 2 gives good diastereoselectivities while the reactions with the E-isomer 3 are non-stereoselective.

aqueous media - Michael additions - radical reactions - stereoselective synthesis - zinc-copper couple

References

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Representative Experimental Procedure: To a solution of the chiral Michael acceptor 1-3 (1 mmol) and alkyl iodide (4, 2 to 6 mmol) in aq EtOH (5 mL, 70%) was added CuI (2 mmol) and Zn (6 mmol). The resulting black mixture was sonicated (45-180 min) until complete consumption of α,β-unsaturated system was achieved (TLC test). The mixture was diluted with EtOAc (8 mL), sonicated during 10 min, and filtered through a short pad of Celite^®, washing the solids with EtOAc (3 × 25 mL). The organic phase was washed with brine (50 mL), dried, filtered, and concentrated in vacuo. The residue was purified by flash chromatography to afford, after concentration, the desired 1,4-addition product.

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