Though Cp*Rh(iii) complexes are prominent and versatile catalysts for C–H bond functionalization reactions, catalytic stereocontrol is difficult due to the lack of vacant coordination sites. Here, we report a hybrid strategy for inducing chirality without using previously reported chiral Cp^x ligands. A preformed hybrid catalyst, [Cp*RhL_N][6,6′-Br-(S)-BINSate], catalysed C–H activation and subsequent conjugate addition of 2-phenylpyridine derivatives to enones in good yield and enantioselectivity (enantiomeric ratio up to 95:5). In addition to 2-phenylpyridines, the conjugate addition of 6-arylpurines proceeded with an enantiomeric ratio of up to 91:9 using [Cp*RhL_N][(R)-SPISate]. The results demonstrate that a chiral organic anion can efficiently control the enantioselectivity of Cp*Rh(iii)-catalysed C–H bond functionalization without a chiral Cp^x ligand.

尽管Cp * Rh（iii）络合物是C-H键官能化反应的重要催化剂，但由于缺乏空位的配位位点，催化立体控制很困难。在这里，我们报告了一种诱导手性而不使用先前报道的手性Cp ^x配体的混合策略。预先形成的杂化催化剂，[Cp * RhL _N ] [ 6,6' -Br-（S）-BINSate]，催化CH-活化，随后将2-苯基吡啶衍生物共轭加成至烯酮，收率和对映选择性（对映体比率）高达95：5）。除2-苯基吡啶外，使用[Cp * RhL _N ] [（R）-SPISate]。结果表明，手性有机阴离子可以有效地控制Cp * Rh（iii）催化的C–H键官能化的对映选择性，而无需手性Cp ^x配体。