(A)  Targeting at alcohol or masked-alcohol-directed C�H functional-ization of aliphatic compounds, we developed a Pd-catalyzed vicinal oxidation of unactivated C�H bonds (non-allylic/aromatic) using alcohol-derived oximes as directing groups. This method permits rapid access of chemically differentiated 1,2-diols from mono-alcohol motifs.(B)  In search for a ketone-directed C�H functional-ization, we first developed a Pd-catalyzed direct �-arylation of ketones using aryl halides. Simple cyclic ketones with different ring-sizes, and acyclic ketones, can be directly arylated at the �-position with complete site-selectivity and high functional group tolerance. Secondly, aiming to alkylate ketones using simple unactivated olefins (alkynes/allenes), we have proposed a transition metal and amine-cocatalyzed C�H functionalization strategy. This strategy is expected to 1) substitute expensive and toxic halogen reactants with cheap, more environmentally benign olefins; 2) allow reactions to occur at neutral and catalytic conditions without stoichiometric strong bases; 3) offer a byproduct-free process. We have developed the first Rh-catalyzed regioselective C-alkylation of 1,2-diketones with simple unactivated olefins, which serves as an important exploratory study. Recently, we achieved breakthroughs on alkylating normal ketones (i.e. cyclopentanones or acetones) with simple olefins or alkynes by employing new catalysts. Thirdly, we have also discovered the first Pd-catalyzed simple ketone-directed C�H hydroxylation of arenes, which provides an efficient way to access various o-acylphenols.(C)   We developed a Catellani-type vicinal C�H amination reaction of arenes with a broad scope and functional group compatibility, which provides complementary site-selectivity from Buchwald�Hartwig aminations.

Site-selective C-H functionalization based on common functional groups

247th National Meeting (2014)

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