Palladium-Catalyzed Arylation of Unactivated γ-Methylene C(sp3)H and δ-CH Bonds with an Oxazoline-Carboxylate Auxiliary

• Published in: Chemistry : a European journal Vol. 21; no. 48; pp. 17503 - 17507
• Main Authors: Ling, Peng-Xiang, Fang, Sheng-Long, Yin, Xue-Song, Chen, Kai, Sun, Bo-Zheng, Shi, Bing-Feng
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 23.11.2015; WILEY‐VCH Verlag
• Subjects: Amines; arylation; Construction; CH activation; directing groups; Esters; Ethers; Functional groups; Halogens; oxazolines; palladium; Substrates; Tolerances; oxazolines; CH activation; palladium; directing groups; arylation
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201502621

A palladium‐catalyzed arylation of unactivated γ‐methylene C(sp3)H and remote δ‐CH bonds by using an oxazoline‐carboxylate directing group has been developed. Arylation occurs with a broad substrate scope and high tolerance of functional groups (i.e., halogen, nitro, cyano, ether, trifluoromethyl, amine, and ester). The oxazoline‐type auxiliary can be removed under acidic conditions. Active construction: A palladium‐catalyzed arylation of unactivated γ‐methylene C(sp3)H and remote δ‐CH bonds is accomplished by using an oxazoline‐carboxylate directing group (see scheme). Arylation occurs with a broad substrate scope and high tolerance of functional groups (i.e., halogen, nitro, cyano, ether, trifluoromethyl, amine, and ester). The oxazoline‐type auxiliary can be removed under acidic conditions.