In contrast to the kinetically favored outward isomerization‐hydrocarbonylation of alkenes, the disfavored inward isomerization‐hydrocarbonylation of alkenes remains an important challenge. Herein, we have developed a novel and effective palladium‐catalyzed inward isomerization‐hydroaminocarbonylation of unactivated alkenes and aniline hydrochlorides for the formation of synthetically valuable α‐aryl carboxylic amides in high yields and high site‐selectivities. The high efficiency of the reaction is attributed to a relay catalysis strategy, in which the Markovnikov‐favored [PdH]‐PtBu3 catalyst is responsible for inward isomerization, while the [PdH]‐Ruphos catalyst is responsible for hydroaminocarbonylation of the resulting conjugated aryl alkenes. The reaction exhibits highly functional group tolerance and provides a new method for formal carbonylation of remote C(sp3)‐H bond.

中文翻译：

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钯催化烯烃的内向异构化氢氨基羰基化

与动力学上有利的烯烃向外异构化-加氢羰基化相比，不利的烯烃内向异构化-加氢羰基化仍然是一个重要的挑战。在此，我们开发了一种新型有效的钯催化未活化烯烃和苯胺盐酸盐的向内异构化-氢氨基羰基化反应，用于以高产率和高位点选择性形成具有合成价值的α-芳基羧酰胺。该反应的高效率归因于中继催化策略，其中马尔可夫尼科夫青睐的[PdH]-PtBu3催化剂负责向内异构化，而[PdH]-Ruphos催化剂负责所得共轭芳基烯烃的氢氨基羰基化。该反应表现出高度的官能团耐受性，为远程C(sp3)-H键的形式羰基化提供了一种新方法。