A practical strategy for the generation of virtually enantiomerically pure bis-cyclometalated iridium(III) complexes is reported. Accordingly, the reactions of [Ir(μ-Cl)(ppy) 2 ] 2 (ppy = cyclometalating 2-phenylpyridine) with (S)-4-tert-butyl-2-(2Ј-hydroxyphenyl)-2-oxazoline [(S)-1a], [Ir(μ-Cl)(pq) 2 ] 2 (pq = cyclometalating 2-phenylquinoline) with (S)-2-(2Ј-hydroxyphenyl)-4-isopropyl-2-oxazoline [(S)-1b], and [Ir(μ-Cl) (pbt) 2 ] 2 (pbt = cyclometalating 2-phenylbenzothiazole) with (S)-2-(2Ј-hydroxyphenyl)-4-isopropyl-2-thiazoline [(S)-1d] afforded diastereomeric mixtures of salicyloxazolinato or sal-[a]
A convenient proline‐ and α‐methylproline‐mediated method for the synthesis of enantiomerically pure bis‐cyclometalated iridium(III) complexes is reported. The reactions of l‐proline or l‐α‐methylproline with [Ir(µ‐Cl)(C^N)2]2 (C^N = cyclometalating 2‐phenylpyridine, 2‐phenylbenzoxazole, or 2‐phenylbenzothiazole ligand) afforded diastereomeric mixtures of intermediate prolinatoiridium(III) complexes from which the Λ‐(S) diastereomers were isolated with excellent diastereomeric purity by washing, precipitation, or crystallization. A subsequent trifluoroacetic acid (TFA) induced substitution of the prolinate ligands with 2,2′‐bipyridine with the retention of configuration provided the chiral‐only‐at‐metal complexes with >99 % ee.
Chiral bis‐cyclometalated octahedral organoiridium(III) complexes were designed to target different classes of enzymes, namely carbonic anhydrases, histone deacetylases, and serine proteases. The stereoselective non‐racemic synthesis of selected complexes was used to study the chiral discrimination of enzyme active sites for enantiomers of propeller‐type octahedral metal complexes. Cases for negligible, modest, and significant chiral discrimination in the interaction of iridium propeller complexes with enzyme active sites were identified.
Invited for the cover of this issue is the team of Prof. Meggers. The cover image shows the Λ and Δ enantiomers of a bis-cyclometalated iridium(III) complex and their corresponding mirror-imaged CD spectra.
The cover picture shows the Λ‐ and Δ‐enantiomers of a bis‐cyclometalated Ir(III) complex and their corresponding mirror‐imaged CD spectra. These non‐racemic complexes and derivatives thereof were obtained by utilizing salicyloxazolines (X = O) and salicylthiazolines (X = S) as chiral auxiliaries (R = tBu or iPr). The background shows the silhouette of Landgrave' s Castle, which sits enthroned above the historic city of Marburg. Details are discussed in the article by E. Meggers et al. on . For more on the story behind the cover research, see the .
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