Dotson, J.; Pérez-Estrada, S.; Garcia-Garibay, M. A., Taming Radical Pairs in Nanocrystalline Ketones: Photochemical Synthesis of Compounds with Vicinal Stereogenic All-Carbon Quaternary Centers, J. Am. Chem. Soc. 2018, 140, 8359-8371, DOI: 10.1021/jacs.8b03988.
Here we describe the use of crystalline ketones to control the fate of the radical pair intermediates generated in the Norrish type I photodecarbonylation reaction to render it a powerful tool in the challenging synthesis of sterically congested carbon?carbon bonds. This methodology makes the synthetically more accessible hexasubstituted ketones ideal synthons for the construction of adjacent, all-carbon substituted, stereogenic quaternary stereocenters. We describe here the structural and thermochemical parameters required of the starting ketone in order to react in the solid state. Finally, the scope and scalability of the reaction and its application in the total synthesis of two natural products is described.