Plenary Session, Award lecture

Photochemical Dearomatization of Nonactivated Arenes

D. Sarlah1
1Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, United States -

Small, heteroatom-containing complex molecules are highly desired in all areas of chemistry, but they are also often difficult to access. Selective transformations of aromatic compounds could provide a more direct route to such desirable targets; however, the many challenges associated with dearomative functionalization have left these types of reactions widely underdeveloped. Our group has been developing new strategies that bridge the gap between dearomatization and alkene chemistry. In pursuit of this goal, we have established dearomative functionalizations using small molecules–arenophiles. Arenophiles photochemically reacts with arenes in [4+2] fashion, enabling reactions of formally isolated alkenes in aromatic substrates. Thus, well-established olefin reactions, such as dihydroxylation and reduction [1], can now be more directly applied to arenes. Additionally, arenophiles in combination with transition metal catalysis provide unique platform [2, 3] and enable the rapid access to a diverse range of products that are both challenging to synthesize via existing methods and complementary to those acquired through biological or chemical dearomative processes. Finally, using this methodology we have recently completed the synthesis of several complex anticancer natural products, including pancratistatins, lycoricidine, and narciclasine [4, 5].

[1] E. H. Southgate, J. Pospech, J. Fu, D. R. Holycross, D. Sarlah, Nature Chem., 2016, 8, 922–928.
[2] M. Okumura, A. S. Shved, D. Sarlah, J. Am. Chem. Soc.,2017,139, 17787–17790.
[3] L. W. Hernandez, U. Klöckner, J. Pospech, L. Hauss, D. Sarlah, J. Am. Chem. Soc., 2018, 140, 4503–4507.
[4] E. H. Southgate, D. R. Holycross, D. Sarlah, Angew. Chem. Int. Ed.,2017,56, 15049–15052.
[5] L. W. Hernandez, J. Pospech, U. Kloeckner, T. W. Bingham, D. Sarlah, J. Am. Chem. Soc., 2017, 139, 15656–15659.