first appeared in 1949, part of Kharasch's studies on peroxide effects. Because chain transfer occurs very slowly, the radical reaction required a very large excess of aldehyde and, with dicarbonyl substrates, decarbonylation byproducts appeared in large quantity.

In the 1970s, metal-catalyzed hydroacylation was discovered for the synthesis of certain prostanoids. The reaction required tin tetrachloride