Fig. 3: Stereodivergence of the 1,3-difunctionalization of alkenes and extension to other product classes.

a, Selected example of syn-selective hydroxyacylation in contrast to anti-configured product 29. b, Scope of anti-selective 1,3-hydroxyacylation, achieved by the addition of DMSO at 35 °C and quenching with tetrabutylammonium bromide at room temperature. c, Additional 1,3-difunctionalization reactions using other nucleophiles—tetrabutylammonium halides, dimethylacetamide, dimethylformamide or TEMPO—at 35 °C. d, 1,4-Dicarbonyl synthesis through Kornblum-type oxidation, employing DMSO at 35 °C, followed by NEt₃ at room temperature. All products were obtained at greater than 20:1 d.r. and 20:1 r.r., unless otherwise mentioned (Supplementary Information). *The reported yields correspond to averages over three runs. In cases in which competing pathways led to observation of enone byproducts in the crude mixtures, the following percentages were observed: ^a5, ^b10, ^c11.