Modulated Aerobic Oxidation Catalysis

Selectivity modulated, oxidation potentially inhibited by ligands 

Valuable ligand effects have been observed in oxidative Heck reactions. Arenes with weak directing groups benefit from the use of amino acid ligands such as acetylated isoleucine (Ac-Ile-OH), which promote C-H activation via proton 

Nitrogen oxide (NO, ) cocatalysts [120] have received industrial interest in Pd-catalyzed aerobic oxidations such as oxidative carbonylation (see Section 8.2.2) [18], alkene oxidation [121], and arene acetoxylation [55]. Recent studies from academic literature have provided new insights into the roles of NO in these reactions. Pd-catalyzed aerobic alkene oxidation (Wacker reaction) typically affords methyl ketones arising from Markovnikov addition of water (or hydroxide) to an 

Conventional Wacker process Markovnikov PdClj/CuCI 

Nitrite-modulated Wacker process Anti-Markovnikov [PdCl2(PhCN)2]/CuCl2/AgN02 

---