Deaminative (Carbonylative) Alkyl‐Heck‐type Reactions Enabled by Photocatalytic C−N Bond Activation

• Published in: Angewandte Chemie International Edition Vol. 58; no. 8; pp. 2402 - 2406
• Main Authors: Jiang, Xuan, Zhang, Mao‐Mao, Xiong, Wei, Lu, Liang‐Qiu, Xiao, Wen‐Jing
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 18.02.2019; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Activation; Aliphatic compounds; Alkenes; Amines; Aromatic compounds; carbonylative reactions; Carbonyls; Catalysis; Chemical reactions; Chemistry; Chemistry, Multidisciplinary; deaminative transformations; Genetic transformation; Heck reaction; Palladium; photocatalysis; Photoredox catalysis; Physical Sciences; Science & Technology; Side reactions; HALIDES; ROOM-TEMPERATURE; carbonylative reactions; amines; deaminative transformations; Heck reaction; BENZYLIC AMINES; FUNCTIONALIZATION; CROSS-COUPLINGS; OLEFINS; GENERATION; ARYL; photocatalysis; METAL-FREE; TRANSFORMATIONS
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201813689

The palladium‐catalyzed Heck reaction is a well‐known, Nobel Prize winning transformation for producing alkenes. Unlike the alkenyl and aryl variants of the Heck reaction, the alkyl‐Heck reaction is still underdeveloped owing to the competitive side reactions of alkyl–palladium species. Herein, we describe the development of a deaminative alkyl‐Heck‐type reaction that proceeds through C−N bond activation by visible‐light photoredox catalysis. A variety of aliphatic primary amines were found to be efficient starting materials for this new process, affording the corresponding alkene products in good yields under mild reaction conditions. Moreover, this strategy was successfully applied to deaminative carbonylative alkyl‐Heck‐type reactions. Single‐electron process: A deaminative alkyl‐Heck‐type reaction and its carbonylative variant proceed through photocatalytic C−N bond activation. This process represents a significant complement to the classic palladium‐catalyzed Heck reaction, and features easily available starting materials, good reaction efficiency, and mild reaction conditions. Tppy=2,4,6‐triphenylpyridine.