Sc(OTf)3-catalyzed diastereoselective Friedel–Crafts reactions of arenes and hetarenes with 3-phenylglycidates?

Organic & Biomolecular Chemistry Pub Date: 2012-07-02 DOI: 10.1039/C2OB25988E

Abstract

Five different para-substituted 3-phenylglycidates (3-phenyloxirane-2-carboxylates) were prepared and subjected to reactions with arenes and hetarenes under Lewis acid catalysis. Sc(OTf)3 was found to effectively (5 mol%) promote a Friedel–Crafts reaction in nitromethane as the solvent. The reaction was shown to proceed stereoconvergently, which makes the intermediacy of a benzylic cation likely. The diastereoselectivities varied depending on the choice of the nucleophile and 3-arylglycidate. Best results were obtained with tert-butyl 3-anisylglycidate, which delivered the respective products with high syn-preference in diastereomeric ratios (d.r.) between 82?:?18 and >95?:?5. The observed selectivity can be explained by a model, according to which the intermediate benzylic cations adopt a preferred conformation, which allows for diastereoface-differentiation by the adjacent stereogenic center.

Graphical abstract: Sc(OTf)3-catalyzed diastereoselective Friedel–Crafts reactions of arenes and hetarenes with 3-phenylglycidates
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