A series of optically-active pseudo-tetrahedral five-membered cyclometalated 1-naphthylethanamine iridium(III) complexes were prepared and characterized to analyze the efficacy of the stereogenic conformational lock in both solid and solution phases. The synthesis of the iridacycles was diastereoselective and the compounds were found to be conformationally rigid. When compared to its phenyl derivative, the structural lock prevented oxidation of the amine moiety within the five-membered organometallic ring during its synthesis. With up to three stereogenic centers in one of the naphthalene complexes, the stereochemistry of the metallacycle remained stable to both thermal and chemical changes. In terms of catalytic performance, the complexes displayed excellent activity for the asymmetric hydrogen transfer reaction, albeit modest enantioselectivities.

A number of palladacycles containing chiral chelating auxiliaries have been utilized as efficient catalysts for asymmetric hydrophosphination reactions. In all cases, the chiral auxiliaries remained coordinated to the palladium centres...

A 1,2‐dihydrophosphination of bis(phenylphosphino)ethane with a wide range of activated olefins was achieved in a catalytic manner with enantiomeric and diastereomeric excess of up to >99% and 44% respectively. The protocol can be extended to selected substrates leading to free P‐ and C‐chiral 1,2‐diphosphines. The synthesized ligands can also undergo direct complexation onto palladium affording complexes with complete retention of stereo‐integrity.

The iridation of (R)-N,N-dimethyl-1-(1-naphthyl)ethylamine in the presence of a base afforded an assortment of products ranging from organic molecules to coordinated systems and cyclometalated complexes. The transformation affirmed the postulation where steric effects within the coordination sphere favor a β-hydride elimination-like decomposition pathway, competing alongside ortho-metalation, thus leading to iminium intermediates. The same procedure also generated an unprecedented carbocyclic η,η-cycloiridated species that could not be attained from the direct cyclometalation of its organic ligand.

Curcumin and its derivatives were successfully functionalized with a series of secondary phosphines via catalytic asymmetric dihydrophosphination to give enantioenriched products with up to 95% enantiomeric excess (ee). Subsequently, the medicinal activities of dihydrophosphinated–curcumin gold­(I) complexes obtained from the in situ complexation of dihydrophosphinated–curcumin with gold­(I) were evaluated using the MKN74 and MCF7 cancer cell lines and compared to existing drugs such as curcumin and cisplatin.