Substrate directed, KCTf3 promoted, enantioselective Heck Matsuda arylations of meso (1R,2S)-cyclohex-4-ene-1,2-diol yielded all cis substituted arylcyclohexenols containing three defined stereocenters. The products were obtained as single diastereomers in moderate to high yields and very high enantioselectivities. The reaction proceeds at mild temperatures and does not require inert atmosphere or dry solvents. In addition, aryl halides were tolerated under reaction conditions allowing for highly functionalized and versatile products. The diastereoselectivity of this desymmetrization reaction is controlled by a non covalent cation-dipole interaction between the cationic palladium and one of the hydroxyl groups. Use of an electron poor N,N ligand, the cationic reaction promoter KCTf3 and an apolar solvent provided optimal results. The stereochemistry of the adducts was confirmed by X-ray diffraction of a carbonate derivative. Moreover, DFT calculations were performed to further investigate the origins of selectivity for this reaction.

Substrate directed, enantioselective Heck arylation of cyclohexenols promoted by KCTf3: Synthesis of all cis substituted, arylcyclohexenols

255th National Meeting (2018)

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