Asymmetric Synthesis of Octahedral Coordination Complexes

In contrast to stereoselective organic chemistry, which has established sophisticated synthetic strategies to control the relative and absolute configuration at tetrahedral carbon atoms, the stereochemical control of octahedral coordination spheres is much less understood. This microreview reflects on the state of the art of asymmetric coordination chemistry of octahedral complexes within the historical context, including asymmetric coordination chemistry evolved by nature, the predetermination of metal‐centered chirality with tailored chiral ligands, chiral‐anion‐mediated asymmetric synthesis, chiral‐auxiliary‐mediated asymmetric coordination chemistry, and finally, very recent work on the catalytic asymmetric synthesis of an octahedral coordination complex. The stereocontrolled synthesis of octahedral metal complexes is an important problem of contemporary coordination chemistry and will ultimately provide the necessary synthetic tools to fully exploit the opportunities provided by the rich stereochemistry of octahedral coordination geometries.