Prenylation is a ubiquitous process common to almost all living organisms, and a key transformation in organic synthesis. Dearomative prenylation reactions of tryptophan derivatives lead to various prenylated indoline alkaloids with diverse biological activities. However, enantioselective dearomative prenylations without a pre-installed stereogenic centre in the substrate have not been reported. Here, we show that a small molecule-based catalytic system derived from a commercially available palladium precursor and a chiral phosphoramidite ligand (allylphos) can catalyse the enantioselective dearomative prenylation of indole derivatives, which tolerates a much broader substrate scope than those of known enzymatic dearomative prenylation processes. Enantioselective dearomative geranylation and farnesylation reactions also proceed smoothly under the standard conditions. The concise total or formal syntheses of a series of natural products can be realized using this catalytic system. The mechanistic investigations provide deep insights for the further design of chiral ligands and catalysts for asymmetric reactions.

烯丙基化是几乎所有活生物体普遍存在的过程，并且是有机合成中的关键转变。色氨酸衍生物的脱芳香性烯丙基化反应导致具有不同生物活性的各种烯丙基化吲哚啉生物碱。然而，尚未报道在底物中没有预先安装立体异构中心的对映选择性脱芳香基异戊烯基。在这里，我们显示了衍生自市售钯前体和手性亚磷酰胺配体（烯丙基磷）的基于小分子的催化系统可以催化吲哚衍生物的对映选择性脱芳香性烯丙基化，与已知的酶脱芳香剂相比，其可耐受的底物范围要广得多异戊烯化过程。在标准条件下，对映选择性脱芳香基香叶基化和法呢基化反应也能顺利进行。使用该催化系统可以实现一系列天然产物的简明的全部或形式合成。机理研究为手性配体和不对称反应催化剂的进一步设计提供了深刻的见解。