Enantioselective oxygenation of exocyclic methylene groups by a manganese porphyrin catalyst with a chiral recognition site

Chem Sci. 2020 Jan 14;11(8):2121-2129. doi: 10.1039/c9sc06089h.

Abstract

The natural enzyme cytochrome P450 is widely recognised for its unique ability to catalyse highly selective oxygen insertion reactions into unactivated C-H bonds under mild conditions. Its exceptional potential for organic synthesis served as an inspiration for the presented biomimetic hydroxylation approach. Via a remote hydrogen bonding motif a high enantioselectivity in the manganese-catalysed oxygenation of quinolone analogues (27 examples, 18-64% yield, 80-99% ee) was achieved. The site-selectivity was completely altered in favour of a less reactive but more accessible position.