Palladium‐Catalyzed Hydroaminocarbonylation of Olefins with Aliphatic Amines without Additives

• Published in: European journal of organic chemistry Vol. 26; no. 31
• Main Authors: Bede, Fanni, Kollár, László, Lambert, Nándor, Huszthy, Péter, Pongrácz, Péter
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 14.08.2023; Wiley Subscription Services, Inc
• Subjects: Additives; Aliphatic amines; Alkenes; Amides; amines; Basicity; carbonylation; Chemical reactions; Chemistry; Chemistry, Organic; homogeneous catalysis; Isoprene; Nucleophiles; Palladium; Physical Sciences; Science & Technology; ALKENES; homogeneous catalysis; amines; Amides; palladium; AMINOCARBONYLATION; carbonylation
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.202300571

Palladium‐catalyzed hydroaminocarbonylation reactions of olefins using aliphatic amines were performed under carbon monoxide atmosphere. Despite the strong basicity of the applied nucleophiles, the targeted amides were successfully synthesized in the absence of acidic additives. Styrene, oct‐1‐ene and isoprene were transformed to the corresponding amide isomers in moderate to good isolated yields under optimized reaction conditions. Various aliphatic amines were used as N‐nucleophiles. The effect of chiral diphosphines on product distribution, that is, on chemo‐, regio‐ and enantioselectivities was also studied. Plausible explanation was given for the additive‐free hydroaminocarbonylation reaction. Hydroaminocarbonylation of olefins with aliphatic amines was successfully performed without acidic additives. Despite the strong basicity of the nucleophiles, targeted amide derivatives of styrene, oct‐1‐ene and isoprene were obtained with high chemo‐ and regioselectivity. Mechanistic considerations were made supported by experimental observations.