Chiral 1,2-diols are commonly found in natural products. Sharpless asymmetric dihydroxylation offers a general means to prepare chiral syn-1,2-diols, but chiral anti-1,2-diols are more troublesome to prepare. One general strategy for the synthesis of chiral anti-1,2-diols is the addition of a carbon nucleophile such as an organomagnesium or -lithium species to an alpha-oxyaldehyde under polar Felkin-Anh control. We demonstrate that alpha-oxyaldehydes generated through organocatalytic, enantioselective alpha-oxygenation are appealing substrates for this process and that the carbon nucleophile additions proceed with anti selectivity, not the previously reported syn selectivity. This method is highly general, with good yield and selectivity observed using a broad range of organomagnesium and -lithium reagents. The strategy was applied to an efficient synthesis of all possible stereoisomers of two oxylipins from Dracontium loretense.

Chiral anti-diols from alpha-oxyaldehydes

249th National Meeting (2015)

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