By virtue of the atom- and step-economy, utilization of simple arenes as a supplant of pre-prepared aryl metal species or aryl halides for the synthesis of arylated chiral molecules has attracted great attention from the synthetic community. While transition-metal-catalyzed enantioselective diarylation of tethered alkenes has been employed to prepare important chiral cyclic compounds, the direct use of simple arenes as aryl precursors is still underdeveloped, probably due to the difficulties in the effective control of the reactivity, site-selectivity and/or enantioselectivity. Herein we report an asymmetric Pd/Ag dual metal catalytic system for the non-directed, site- and enantioselective domino Heck/intermolecular C–H functionalization of arenes. Mechanistic studies showed that Pd and Ag act in cooperation in the catalysis and the chiral bisphosphine ligand plays a bifunctional role, i.e., assisting the silver species in the cleavage of the aryl C–H bond, while inducing the enantioselectivity on direct complexation with palladium. This method provides an efficient approach to the corresponding chiral oxindoles with good enantiomeric excesses from a broad scope of arenes, including fluoroarenes, heteroarenes and several complex products derived from medicines or natural products.

凭借原子经济和步骤经济，利用简单芳烃作为预先制备的芳基金属物种或芳基卤化物的替代品来合成芳基化手性分子引起了合成界的高度关注。虽然过渡金属催化的束缚烯烃的对映选择性二芳基化已被用来制备重要的手性环状化合物，但直接使用简单的芳烃作为芳基前体仍然不发达，这可能是由于反应活性、位点选择性的有效控制存在困难。和/或对映选择性。在此，我们报道了一种用于芳烃非定向、位点和对映选择性多米诺赫克/分子间C-H功能化的不对称Pd/Ag双金属催化系统。机理研究表明，Pd和Ag在催化中协同作用，手性双膦配体发挥双功能作用，即协助银物种裂解芳基C-H键，同时诱导与钯直接络合的对映选择性。该方法提供了一种有效的方法，从广泛的芳烃中获得具有良好对映体过量的相应手性羟吲哚，包括氟芳烃、杂芳烃和源自药物或天然产物的几种复杂产物。