Cross‐Coupling–Elimination Reactions Mediated or Catalyzed by Zirconium Complexes: A Valuable Tool in Organic Synthesis

Abstract

The tandem zirconocene-mediated or -catalyzed cross-coupling-elimination reaction provides an efficient and versatile procedure for the construction of scaffolds that in many cases are difficult to access by traditional organic chemistry. In general, this process supposes the reaction of two unsaturated molecules. One of them is coordinated to the zirconocene and the other one contains a heteroatom at an appropriate position for the subsequent elimination process.

Zirconium oxo clusters as discrete molecular catalysts for the direct amide bond formation

“…1,2 In addition, organozirconium species, frequently generated by hydrozirconation reactions, have a highly polarized Zr–C bond, and their ability to undergo a transmetalation step has been leveraged for the total synthesis of many complex molecules. 3–8 Yet, Zr( iv ) strong Lewis acidity and the characteristic oxophilicity of group (IV) metals still pose a challenge for its broader use, due to the regular need for inert and dry conditions in order to avoid Zr catalyst decomposition, and secure good overall efficiency for the desired transformation. 9 Thus, more robust zirconium catalysts with tunable reactivity bear the potential to boost their synthetic utility, which is an important goal in sustainable chemistry, considering the greater abundance of zirconium compared to many other transition metals commonly employed in catalysis.…”