Toluene and its derivatives are petroleum-derived raw materials produced from gasoline by catalytic reformation. These abundant chemical feedstocks are commonly used as solvents in organic synthesis. The C(sp³)−H functionalization of these unactivated substrates has been widely used to directly introduce benzylic motifs into diverse molecules to furnish important compounds. Despite these advances, progress in asymmetric catalysis remains underdeveloped. Here, we report photoinduced radical-based enantioselective C(sp³)−C(sp³) coupling reactions of activated ketones with toluene and its derivatives by means of chiral acid catalysis. With a La(OTf)₃/pybox complex catalyst, a variety of chiral 3-hydroxy-3-benzyl-substituted 2-oxindoles, including many conventionally difficult-to-access variants, are obtained directly from isatins in high yields with good to excellent enantioselectivities. Acenaphthoquinone is also compatible with the use of a chiral phosphoric acid (CPA) catalyst, leading to another series of important enantioenriched tertiary alcohols.

甲苯及其衍生物是通过催化重整从汽油生产的石油衍生原料。这些丰富的化学原料通常用作有机合成中的溶剂。这些未激活的底物的C（sp ³）-H功能化已被广泛用于将苄基基序直接引入各种分子中，以提供重要的化合物。尽管取得了这些进展，但不对称催化的进展仍未得到开发。在这里，我们报告通过手性酸催化的活化酮与甲苯及其衍生物的光诱导的基于自由基的对映选择性C（sp ³）-C（sp ³）偶联反应。有La（OTf）₃/ pybox络合催化剂，是由手性异构体直接以高收率和良好或优异的对映选择性获得的手性3-羟基-3-苄基取代的2-羟吲哚，包括许多常规上难以接近的变体。ena苯醌还与手性磷酸（CPA）催化剂的使用兼容，从而产生了另一系列重要的对映体富集的叔醇。