The functionalization of carbon–hydrogen bonds offers an attractive step-economical entry into valuable organic intermediates from simple hydrocarbon precursors. The recent research of our group has focused on the development of various transition-metal-catalyzed methods for the functionalization of non-activated C(sp3)–H and C(sp2)–H bonds.
The reactions that we have developed allow the formation of C(sp3)–C(sp2) bonds from simple C(sp2)–X/C(sp3)–H precursors (X = leaving group) using palladium catalysts. A variety of valuable carbocycles and heterocycles are generated through these methods.
Review: Acc. Chem. Res. 2017, 50, 1114.
Leading papers: Angew. Chem. Int. Ed. 2003, 42, 5736; J. Am. Chem. Soc. 2008, 130, 15157; J. Am. Chem. Soc. 2010, 132, 10706; Angew. Chem. Int. Ed. 2012, 51, 10399; Angew. Chem. Int. Ed. 2016, 55, 2805; Angew. Chem. Int. Ed. 2017, 56, 7218; Angew. Chem. Int. Ed. 2018, 57, 12131.
Functionalization of distant C–H bonds
Recently, we employed the 1,4-Pd shift strategy to reach more distant C(sp3)–H bonds and create both C(sp2)–C(sp3) and C(sp3)–C(sp3) bonds.
We are developing enantioselective C(sp3)–H and C(sp2)–H activation reactions using various types of chiral catalysts. These methods allow access to enantioenriched molecules with potential applications in medicinal chemistry or chiroptical devices.
Synthesis of natural products
Multiple C–H activation allows to streamline the synthesis of bioactive natural products using simpler precursors. Using such strategies, we recently synthesized:
- aeruginosins (e. g., aeruginosin 298A), cyanotoxins isolated from various blue-green algae;
- lycorine alkaloids, originated from Amaryllidaceae plants (e. g., γ-lycorane);
- (nor)illudalane sesquiterpenes (e. g., puraquinonic acid and russujaponol F), isolated from various species of higher fungi;
- pentacyclic dithiodiketopiperazines (e. g., epicoccin G and rostratin A), isolated from various types of fungi.