Studies on transition metal-catalyzed C-H functionalization of biologically useful scaffolds

Abstract

Part 1. $Rh^I$ -Catalyzed Site-Selective Decarbonylative Alkenylation and Arylation of Quinolones

An efficient catalytic system for the C2 selective C？H functionalization of N-pyrimidyl-4-quinolones was developed using a decarbonylative coupling mechanism. The installation of an N-pyrimidyl group on the quinolone nitrogen atom redirected the coordination between the catalyst and the carbonyl group to promote direct C？H functionalization at the C2-position of 4-quinolones intstead of C5. In addition, the present pro-tocol was successfully applied to the C3 selective installation of a variety of aryl and vinyl groups on an iso-quinolone scaffold.

Keywords : decarbonylative coupling, C-H functionalization, quinolone, isoquinolone

Part 2. Pd-Catalyzed Asymmetric Decarboxylative Allylation of Morpholinones: Strategy for Chiral Morpholine and Unnatural Amino Acid Synthesis

We tried to develop an enantioselective reaction to yield quaternary chiral center using palladium(0) catalyzed decarboxylative allylation. Using this asymmetric method, introducing a quaternary chiral center onto C3 position of morpholine derivatives. During this research, we were able to introduce new PHOX type ligand which modifies enantioselectivity.

Keywords : decarboxylative allylation, chiral quaternary center, morpholine, morpholinone

Part 3. Pd-Catalyzed One-Pot Synthesis of 6-Aryl-2-α-styrylpyridines with Triazolopyridines

We developed a new strategy for Pd-catalyzed synthesis of 6-aryl-2-α-styrylpyridines from tria-zolopyridines, wherein switchable chemical transformations (C3 vs C7) is observed by differentiating sub-strates using different bases. Two separate arylation catalyses were successfully performed in a tandem se-quence, providing convenient access to 6-aryl-2-α-styrylpyridines with various triazolopyridines.