Palladium complexes carbon/oxygen additions

Oxidative addition involving carbon-to-oxygen bonds is of relevance to the catalysis with palladium complexes. The most reactive carbon-oxygen bond is that between allylic fragments and carboxylates. The reaction starts with a palladium zero complex and the product is a ir-allylic palladium(II) carboxylate Figure 2.16. 

C-M bond addition, for C-C bond formation, 10, 403-491 iridium additions, 10, 456 nickel additions, 10, 463 niobium additions, 10, 427 osmium additions, 10, 445 palladium additions, 10, 468 rhodium additions, 10, 455 ruthenium additions, 10, 444 Sc and Y additions, 10, 405 tantalum additions, 10, 429 titanium additions, 10, 421 vanadium additions, 10, 426 zirconium additions, 10, 424 Carbon-oxygen bond formation via alkyne hydration, 10, 678 for aryl and alkenyl ethers, 10, 650 via cobalt-mediated propargylic etherification, 10, 665 Cu-mediated, with borons, 9, 219 cycloetherification, 10, 673 etherification, 10, 669, 10, 685 via hydro- and alkylative alkoxylation, 10, 683 via inter- andd intramolecular hydroalkoxylation, 10, 672 via metal vinylidenes, 10, 676 via SnI and S Z processes, 10, 684 via transition metal rc-arene complexes, 10, 685 via transition metal-mediated etherification, overview,... 

Reductive eliminations from nickel(ll) complexes to form carbon-heteroatom bonds in amines and ethers have also been reported. Like the mechanisms for oxidative additions to Ni(0) and Pd(0) that cleave carbon-heteroatom bonds, the mechanisms for reductive elimination from nickel(II) and palladium(II) complexes to form caibon-heteroatom bonds are different from each other. Most reductive eliminations from Ni(II) to form carbon-nitrogen bonds occur after oxidation of the Ni(II) to Ni(III) with ferro-ceruum, oxygen, or iodine (Equations 8.53 and 8.54). Reductive eliminations from Ni(II) to form carbon-oxygen bonds in ethers also requires oxidation of ttie Ni(II) to Ni(III) (Equation 8.55). In contrast, reductive eliminations from Ni(II) to form the ester group of a lactone occurred after a proposed insertion of CO into the nickel-carbon bond of an oxametallacycle without oxidation. Reductive eliminations from isolated arylnickd complexes to form amines and ethers have not been reported. 

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