title: Chemoselective Transformation of Diarylethanones to Arylmethanoic Acids and Diarylmethanones and Mechanistic Insights.
abstract: The chemoselective transformation of diarylethanones via either aerobic oxidative cleavage to give arylmethanoic acids or tandem aerobic oxidation/benzilic acid rearrangement/decarboxylation to give diarylmethanones has been developed. The transformation is controllable and applicable to a broad spectrum of substrates and affords the desired products in good to excellent yields. Mechanistic insights with control reactions, (1)H NMR tracking, and single-crystal X-ray diffraction reveal a complex mechanistic network in which two common intermediates, α-ketohydroperoxide and diarylethanedione, and three plausible pathways are proposed and verified. These pathways are interlinked and can be switched reasonably by changing the reaction conditions. This method enables scalable synthesis and access to a number of valuable compounds, including vitamin B3, diphenic acid, and the nonsteroidal anti-inflammatory drug ketoprofen. The present protocol represents a step forward in exploiting complex mechanistic networks to control reaction pathways, achieving divergent syntheses from the same class of starting materials.
authors.affiliation: Key Laboratory of Pesticide & Chemical Biology of the Ministry of Education, College of Chemistry, Central China Normal University , Wuhan 430079, P. R. China.
authors.forename: Xing
authors.initials: X
authors.lastname: Wang
authors.affiliation: Key Laboratory of Pesticide & Chemical Biology of the Ministry of Education, College of Chemistry, Central China Normal University , Wuhan 430079, P. R. China.
authors.forename: Rui-Xi
authors.initials: RX
authors.lastname: Chen
authors.affiliation: Key Laboratory of Pesticide & Chemical Biology of the Ministry of Education, College of Chemistry, Central China Normal University , Wuhan 430079, P. R. China.
authors.forename: Zeng-Feng
authors.initials: ZF
authors.lastname: Wei
authors.affiliation: Key Laboratory of Pesticide & Chemical Biology of the Ministry of Education, College of Chemistry, Central China Normal University , Wuhan 430079, P. R. China.
authors.forename: Chen-Yang
authors.initials: CY
authors.lastname: Zhang
authors.affiliation: Key Laboratory of Pesticide & Chemical Biology of the Ministry of Education, College of Chemistry, Central China Normal University , Wuhan 430079, P. R. China.
authors.forename: Hai-Yang
authors.initials: HY
authors.lastname: Tu
authors.affiliation: Key Laboratory of Pesticide & Chemical Biology of the Ministry of Education, College of Chemistry, Central China Normal University , Wuhan 430079, P. R. China.
authors.forename: Ai-Dong
authors.initials: AD
authors.lastname: Zhang