In the past few decades, processes that involve transition-metal catalysis have represented am ajor parto f the synthetic chemist'st oolbox. Recently,t he interesth as shifted from the well-established cross-coupling reactions to CÀHb ond functionalization, thus making it ac urrent frontier of transition-metal-catalyzed reactions. Constant progress in this field has led to the discoveryo fe nantioselective methods to generate and control various types of stereogenic elements, thereby demonstrating its high value to generate scalemic chiral molecules.The present review is dedicated to enantioselective Pd 0-catalyzed CÀHa ctivation,w hich may be considered as an evolution of Pd 0-catalyzed cross-couplings, with af ocus on the different chiral ligands and catalysts that enable theset ransformations.
A ligand-controlled site-selective C(sp 3 )À H arylation of heteroaromatic ketones has been developed using Pd catalysis. The reaction occurred selectively at the αor βposition of the ketone side-chain. The switch from αto βarylation was realized by addition of a pyridone ligand. The αarylation process showed broad scope and high site-and chemoselectivity, whereas the β-arylation was more limited. Mechanistic investigations suggested that α-arylation occurs through CÀ H activation/oxidative addition/reductive elimination whereas β-arylation involves desaturation and aryl insertion.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.