Highlightsd The BTB domain of MIZ1 harbors an atypical peptide binding site.d This binding site requires flexibility in a core element of the BTB fold.d Peptide binding selects for homodimers over heterodimers of the MIZ1 BTB domain.
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.
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