title: Transition-metal-free formal decarboxylative coupling of α-oxocarboxylates with α-bromoketones under neutral conditions: a simple access to 1,3-diketones.
abstract: A transition-metal-free formal decarboxylative coupling reaction between α-oxocarboxylates and α-bromoketones to synthesize 1,3-diketone derivatives is presented. In this reaction, a broad scope of substrates can be employed, and neither a metal-based reagent nor an additional base is required. DFT calculations reveal that this reaction proceeds through a coupling followed by decarboxylation mechanism and the α-bromoketone unprecedentedly serves as a nucleophile under neutral conditions. The rate-determining step is an unusual hydrogen-bond-assisted enolate formation by thermolysis.
authors.affiliation: Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, and State Key Laboratory of Biotherapy, West China Medical School, Sichuan University, 29 Wangjiang Road, Chengdu 610064 (P. R. China).
authors.forename: Zhen
authors.initials: Z
authors.lastname: He
authors.forename: Xiaotian
authors.initials: X
authors.lastname: Qi
authors.forename: Shiqing
authors.initials: S
authors.lastname: Li
authors.forename: Yinsong
authors.initials: Y
authors.lastname: Zhao
authors.forename: Ge
authors.initials: G
authors.lastname: Gao
authors.forename: Yu
authors.initials: Y
authors.lastname: Lan
authors.forename: Yiwei
authors.initials: Y
authors.lastname: Wu
authors.forename: Jingbo
authors.initials: J
authors.lastname: Lan
authors.forename: Jingsong
authors.initials: J
authors.lastname: You
mesh_terms: D002264:Carboxylic Acids / Q000737:chemistry*; D002384:Catalysis; D003653:Decarboxylation; D006860:Hydrogen Bonding; D007659:Ketones / Q000737:chemistry*; D013816:Thermodynamics; D028561:Transition Elements / Q000737:chemistry
chemical_list: D002264:Carboxylic Acids; D007659:Ketones; D028561:Transition Elements
keywords: cross-coupling; decarboxylation; enolates; homogeneous catalysis; synthetic methods