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A palladium-catalyzed cross-coupling between aryl esters and anilines is reported, enabling access to diverse amides. The reaction takes place via activation of the C–O bond by oxidative addition with a Pd–NHC complex, which enables the use of relatively non-nucleophilic anilines that otherwise require stoichiometric activation with strong bases in order to react. High yields of aromatic, aliphatic, and heterocyclic products are obtained. A range of activated esters are evaluated in the presence and absence of catalyst, demonstrating that the catalytic methodology substantially increases the types of electrophiles that can be utilized for amide bond formation in the absence of harsh bases.

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A highly regioselective and efficient base‐catalyzed intramolecular hydroalkoxylation of primary and secondary alkynyl alcohols was developed to afford 1,4‐oxaza heterocycles. Although the rates of cyclization for terminal alkynyl alcohols were significantly greater than those for internal ones, our method tolerated both terminal and internal alkynes. In addition, an unprecedented one‐pot hydroamination reaction was found to proceed with high chemo‐ and regioselectivity to form indole‐fused azlactones in the presence of base.

An intermolecular coupling of primary alcohols and organotriflates has been developed to provide ketones by the action of a Ni(0) catalyst. This oxidative transformation is proposed to occur by the union of three distinct catalytic cycles. Two competitive oxidation processes generate aldehyde in situ via hydrogen transfer oxidation or (pseudo)­dehalogenation pathways. As aldehyde forms, a Ni-catalyzed carbonyl-Heck process enables formation of the key carbon–carbon bond. The utility of this rare alcohol to ketone transformation is demonstrated through the synthesis of diverse complex and bioactive molecules.

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