title: Palladium-catalyzed C-H functionalization of acyldiazomethane and tandem cross-coupling reactions.
abstract: Palladium-catalyzed C-H functionalization of acyldiazomethanes with aryl iodides has been developed. This reaction is featured by the retention of the diazo functionality in the transformation, thus constituting a novel method for the introduction of diazo functionality to organic molecules. Consistent with the experimental results, the density functional theory (DFT) calculation indicates that the formation of Pd-carbene species in the catalytic cycle through dinitrogen extrusion from the palladium ethyl diazoacetate (Pd-EDA) complex is less favorable. The reaction instead proceeds through Ag2CO3 assisted deprotonation and subsequently reductive elimination to afford the products with diazo functionality remained. This C-H functionalization transformation can be further combined with the recently evolved palladium-catalyzed cross-coupling reaction of diazo compounds with aryl iodides to develop a tandem coupling process for the synthesis of α,α-diaryl esters. DFT calculation supports the involvement of Pd-carbene as reactive intermediate in the catalytic cycle, which goes through facile carbene migratory insertion with a low energy barrier (3.8 kcal/mol).
authors: †Beijing National Laboratory of Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871 China.
authors: Fei
authors: F
authors: Ye
authors: ‡School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.
authors: Shuanglin
authors: S
authors: Qu
authors: §School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
authors: Lei
authors: L
authors: Zhou
authors: †Beijing National Laboratory of Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871 China.
authors: Cheng
authors: C
authors: Peng
authors: †Beijing National Laboratory of Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871 China.
authors: Chengpeng
authors: C
authors: Wang
authors: †Beijing National Laboratory of Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871 China.
authors: Jiajia
authors: J
authors: Cheng
authors: †Beijing National Laboratory of Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871 China.
authors: Mohammad Lokman
authors: ML
authors: Hossain
authors: †Beijing National Laboratory of Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871 China.
authors: Yizhou
authors: Y
authors: Liu
authors: †Beijing National Laboratory of Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871 China.
authors: Yan
authors: Y
authors: Zhang
authors: ‡School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.
authors: Zhi-Xiang
authors: ZX
authors: Wang
authors: †Beijing National Laboratory of Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871 China.
authors: Jianbo
authors: J
authors: Wang
mesh_terms: D001391:Azo Compounds / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D006859:Hydrogen / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D010165:Palladium / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D001391:Azo Compounds; D010165:Palladium; D002244:Carbon; D006859:Hydrogen