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This paper describes a new method for the transannular functionalization of the γ-C-H bonds in alicyclic amines to install C(sp3 )-halogen, oxygen, nitrogen, boron, and sulfur bonds. The key challenge for this transformation is controlling the relative rate of Cγ -H versus Cα -H functionalization. We demonstrate that this selectivity can be achieved by pre-complexation of the substrate with Pd prior to the addition of oxidant. This approach enables the use of diverse oxidants that ultimately install various heteroatom functional groups at the γ-position with high site- and diastereoselectivity.

A Cu-mediated ortho-C-H radiofluorination of aromatic carboxylic acids that are protected as 8-aminoquinoline benzamides is described. The method uses K18 F and is compatible with a wide range of functional groups. The reaction is showcased in the high specific activity automated synthesis of the RARβ2 agonist [18 F]AC261066.

The direct functionalization of C H bonds has frequently been deemed a “Holy Grail” of organometallic chemistry. A seminal example of this transformation was the demonstration by Shilov and co-workers that platinum(II) salts catalyze the direct oxidation of alkanes into their corresponding alcohols and alkyl halides. Subsequent work in this area has focused on surveying diverse ligands for these reactions in an effort to enhance reactivity and selectivity, slow catalyst decomposition, and replace platinum(IV)-based oxidants with more cost-effective alternatives. In a key development, chemists at Catalytica identified [bpymPtCl2] (bpym= bipyrimidine) as a pre-catalyst for the oxidation of CH4 into CH3OSO3H in fuming H2SO4 (Scheme 1). [5] The reaction