Palladium‐Catalyzed Inward Isomerization Hydroaminocarbonylation of Alkenes

• Published in: Angewandte Chemie International Edition Vol. 63; no. 26; pp. e202406226 - n/a
• Main Authors: Zou, Xian‐Jin, Jin, Zhao‐Xing, Yang, Hui‐Yi, Wu, Fei, Ren, Zhi‐Hui, Guan, Zheng‐Hui
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 21.06.2024; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Alkenes; amide formation; Amides; Aniline; Aromatic compounds; carbon monoxide; Carbonyls; Catalysis; Catalysts; Chemistry; Chemistry, Multidisciplinary; Functional groups; Hydrochlorides; Hydrogen bonds; Isomerization; isomerization-hydrocarbonylation; Palladium; palladium catalysis; Physical Sciences; Science & Technology; sp3 C−H bond carbonylation; CHAIN-WALKING; palladium catalysis; isomerization-hydrocarbonylation; ALKOXYCARBONYLATION; carbon monoxide; ADIPIC ACID; CARBONYLATION; INTERNAL ALKENES; amide formation; sp3 C-H bond carbonylation; OLEFINS; CYCLOISOMERIZATION; ACID-ESTERS; HYDROARYLATION; HYDROFORMYLATION; sp3 C−H bond carbonylation
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202406226

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. A novel palladium‐catalyzed inward isomerization and hydraminocarbonylation of unactivated alkenes for the synthesis of α‐aryl carboxylic amides has been developed. The combination isomerization‐responsible catalyst and hydrocarbonylation‐responsible catalyst was found to be a highly effective strategy to render the reaction feasible. The reaction shows highly functional group compatibility and site‐selectivity.