Oxime palladacycles revisited: stone‐stable complexes nonetheless very active catalysts

Our review critically presents the main achievements, advantages, and limitations of oxime palladacycles as high‐turnover catalysts for Heck, as well as homo‐ and cross‐coupling reactions such as Suzuki–Miyaura, Stille, Ullmann‐type, Cassar–Heck–Sonogashira, sila‐Sonogashira, Glaser‐type, Hiyama, and alkoxycarbonylation reactions. New developments in this area are reviewed from a mechanistic and synthetic point of view. The role of oxime palladacycles as a source of highly active zero‐valent palladium species is also discussed.