转自：康龙化成
Ligand-Enabled ortho-Selective C−HOlefination of Tertiary Aniline Derivatives
Chunchen Yuan,* Changbo Jia, Xinyu Zhang, Wenlong Zhang, Yang’en You, Xiaolong Xu, Lei Zhu, Yiliang Chen, Yongping Dong,* and Liang Xu*
School of Chemistry and ChemicalEngineering Xiushan Campus, Anhui University of Technology, Ma’anshan, Anhui 243032, China; Key Laboratory forGreen Processing of Chemical Engineering of Xinjiang Bingtuan, School ofChemistry and Chemical Engineering, Shihezi University, Shihezi,Xinjiang 832003, China;
Anhui Province Key Laboratory of Advanced CatalyticMaterials and Reaction Engineering, School of Chemistry and ChemicalEngineering, Hefei University of Technology, Hefei, Anhui 230009, China;
—Org.Lett., 2024,26, 4877-4881.
Recommended by Dengfeng Yue_PDM
ABSTRACT:Ahighly ortho-selective CAr−H olefination of tertiary anilineswithout a directing group was developed. This reaction tolerated varioussubstituted arenes and olefin coupling partners, affording ortho-olefinationproducts in moderate to good yields. Preliminary mechanistic studies showedthat N-Ac-D-Ala, Ag2CO3, andBQ were the key factors for tuning the regioselectivity from para to ortho.Density functional theory was used to achieve a theoretical understanding ofthe ortho selectivity.
Metal-CatalyzedC−H Functionalization of Tertiary Anilines
Scope of Anilines
Scope of Olefins
Chunchen Yuan etal developed a ligand-enabled palladium catalyzed ortho-selective C−H olefinationof tertiary anilines. This method provides an efficient approach to access olefinatedtertiary anilines with excellent ortho selectivity. Preliminary mechanisticstudies indicated that N-Ac-D-Ala, Ag2CO3, and BQ were the key factors inrealizing the ortho-selective olefination of tertiary anilines reported here.DFT calculations revealed a weak stabilization interaction between thesubstrate and ligands to achieve ortho-selective C−H activation.
