title: Pd(II)-catalysed meta-C-H functionalizations of benzoic acid derivatives.
abstract: Benzoic acids are highly important structural motifs in drug molecules and natural products. Selective C-H bond functionalization of benzoic acids will provide synthetically useful tools for step-economical organic synthesis. Although direct ortho-C-H functionalizations of benzoic acids or their derivatives have been intensely studied, the ability to activate meta-C-H bond of benzoic acids or their derivatives in a general manner via transition-metal catalysis has been largely unsuccessful. Although chelation-assisted meta-C-H functionalization of electron-rich arenes was reported, chelation-assisted meta-C-H activation of electron-poor arenes such as benzoic acid derivatives remains a formidable challenge. Herein, we report a general protocol for meta-C-H olefination of benzoic acid derivatives using a nitrile-based sulfonamide template. A broad range of benzoic acid derivatives are meta-selectively olefinated using molecular oxygen as the terminal oxidant. The meta-C-H acetoxylation, product of which is further transformed at the meta-position, is also reported.
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian 350002, China.
authors.forename: Shangda
authors.initials: S
authors.lastname: Li
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian 350002, China.
authors.forename: Lei
authors.initials: L
authors.lastname: Cai
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian 350002, China.
authors.forename: Huafang
authors.initials: H
authors.lastname: Ji
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian 350002, China.
authors.forename: Long
authors.initials: L
authors.lastname: Yang
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian 350002, China.|Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, CAS, Fujian 350002, China.
authors.forename: Gang
authors.identifier: http://orcid.org/0000-0001-5229-554X
authors.initials: G
authors.lastname: Li
mesh_terms: D019817:Benzoic Acid / Q000138:chemical synthesis / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D006859:Hydrogen / Q000737:chemistry*; D015394:Molecular Structure; D010100:Oxygen / Q000737:chemistry; D010165:Palladium / Q000737:chemistry*
chemical_list: D010165:Palladium; D002244:Carbon; D006859:Hydrogen; D019817:Benzoic Acid; D010100:Oxygen
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