Photocatalyzed Carbon−Carbon Bond Formation Between Glycerol and Electron-Deficient Olefins

Glycerol is produced in large quantities as a co-product in the manufacturing of biodiesel and has received relatively little attention as a substrate for carbon−carbon bond-forming reactions. In this work, the photocatalyzed reaction between glycerol and electron-deficient olefins is investigated to regioselectively insert an alkyl group at C2 in the triol. The results show that the transformation is highly dependent on the nature of the photocatalyst and the olefin. In the presence of an iridium catalyst and quinuclidine, glycerol can be coupled at C2 with sterically unhindered acrylates. In the presence of tetrabutylammonium decatungstate, glycerol can be reacted with fumaronitrile, N-methyl maleimide, methyl acrylate and itaconic anhydride where the latter two substrates require the additional presence of potassium persulfate as an oxidant. These findings give rise to several new carbon−carbon bond-forming reactions with glycerol that allow the triol to be converted into more elaborate structures.