Cyclopropanation of Allylic Alcohols using Substituted Haloalkylzinc Reagents: Synthesis of gem-Dimethylcyclopropanes

Abstract

gem-Dimethylcyclopropanes were obtained by a cyclopropanation of allylic alcohols and ethers using a mixture of diethylzinc and 2,2-diiodopropane in 53-96% yields. Enantioenriched gem-dimethylcyclopropanes were also synthesized using a glucose-derived auxiliary.

cyclopropanation - gem-dimethylcyclopropanes - carbenoids - chiral auxiliaries - stereoselective synthesis

References

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Charette, A. B.; Wilb, N. unpublished results.

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Typical Experimental Procedure: To a solution of the alkene (0.4 mmol) in anhyd CH₂Cl₂ (16 mL) at -10 °C was added dropwise Et₂Zn (1.6 mmol, 1.2 mmol in the case of the ethers). After 10 min of stirring at that temperature, 2,2-diiodopropane (1.6 mmol, 1.2 mmol in the case of the ethers) was added dropwise over 2 min and the solution was stirred overnight at r.t. The formation of a precipitate (probably ZnI₂) was rapidly observed. The solution was then diluted with ether (10 mL) and washed with 10% aq HCl (10 mL), sat. aq Na₂SO₃ (10 mL), brine (10 mL), dried over MgSO₄, filtered and concentrated under reduced pressure.The crude cyclopropanes were purified by flash chromatography on silica gel.

Recent results showed that these carbenoids are very reactive even with unfunctionalized olefins:

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