Diverse Approaches for Enantioselective C-H Functionalization Reactions Using Group†9 Cpx MIII Catalysts.

Transition-metal-catalyzed C-H functionalization reactions with Cp*MIII catalysts (M=Co, Rh, Ir) have found a wide variety of applications in organic synthesis. Albeit the intrinsic difficulties in achieving catalytic stereocontrol using these catalysts due to their lack of additional coordination sites for external chiral ligands and the conformational flexibility of the Cp ligand, catalytic enantioselective C-H functionalization reactions using the Group 9 metal triad with Cp-type ligands have been intensively studied since 2012. In this minireview, the progress in these reactions according to the type of the chiral catalyst used are summarized and discussed. The development of chiral Cpx ligands the metal complexes thereof, artificial metalloenzymes, chiral carboxylate-assisted enantioselective C-H activations, enantioselective alkylations assisted by chiral carboxylic acids or chiral sulfonates, and chiral transient directing groups are discussed.

Synthesis of 1,1'-Spirobiindane-7,7'-Disulfonic Acid and Disulfonimide: Application for Catalytic Asymmetric Aminalization.

1,1'-Spirobiindane-7,7'-disulfonic acid (SPISA) and 1,1'-spirobiindane-7,7'-disulfonimide were synthesized from 1,1'-spirobiindane-7,7'-diol (SPINOL) in 4 steps using a Pd-catalyzed Newman-Kwart rearrangement as a key step. These new catalysts possessing a rigid spirocyclic backbone were evaluated in a catalytic asymmetric aminalization reaction, and SPISA/iPr2 NEt exhibited high enantioselectivity, demonstrating the utility of SPISA as a chiral Brønsted acid catalyst.