PdII-Catalyzed ?-C(sp3)-H (Hetero)arylation of Ketones Enabled by Transient Directing Groups

被引：18
|
作者：
Li, Yi-Hao [1 ]
Ouyang, Yuxin [1 ]
Chekshin, Nikita [1 ]
Yu, Jin-Quan [1 ]
机构：
[1] Scripps Res Inst, Dept Chem, La Jolla, CA 92037 USA
来源：
ACS CATALYSIS | 2022年 / 12卷 / 17期
关键词：
C-H activation; palladium; ketones; transient directing group; arylation; pyridone ligands; palladacycle; C-H ARYLATION; C(SP(3))-H ARYLATION; INTERMOLECULAR AMIDATION; AMINO AMIDE; FUNCTIONALIZATION; ALDEHYDES; BONDS; ALKYLATION; AUXILIARY;
D O I：
10.1021/acscatal.2c03400
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
Pd(II)-catalyzed gamma-C(sp3)-H (hetero)arylation of aliphatic ketones is developed using alpha-amino acids as transient directing groups (TDG). A variety of aliphatic ketones were (hetero)arylated at the gamma-position via a 5,6-membered fused cyclopalladation intermediate to afford the remotely arylated products in up to 88% yield. The crucial ligand effect of 2-pyridone is further enhanced by reducing the loading of acid additives. Consequentially, the improved reactivity of this catalytic system has also made possible the cyclic gamma-methylene C(sp3)-H arylation of ketones. Mechanistic investigation and comparison to the gamma-C-H arylation of aldehydes revealed a structural insight for designing site-selective TDG.
引用
收藏
页码：10581 / 10586
页数：6
相关论文
共 50 条
  • [1] PdII-Catalyzed Enantioselective C(sp3)-H Arylation of Cyclobutyl Ketones Using a Chiral Transient Directing Group
    Xiao, Li-Jun
    Hong, Kai
    Luo, Fan
    Hu, Liang
    Ewing, William R.
    Yeung, Kap-Sun
    Yu, Jin-Quan
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2020, 59 (24) : 9594 - 9600
  • [2] PdII-Catalyzed Enantioselective C(sp3)–H Arylation of Cyclobutyl Ketones Using a Chiral Transient Directing Group
    Xiao, Li-Jun
    Hong, Kai
    Luo, Fan
    Hu, Liang
    Ewing, William R.
    Yeung, Kap-Sun
    Yu, Jin-Quan
    Advanced Materials, 2020, 59 (24) : 9681 - 9687
  • [3] PdII-Catalyzed Site-selectiveβ- andγ-C(sp3)-H Arylation of PrimaryAldehydes Controlled by Transient Directing Groups
    Li, Yi-Hao
    Ouyang, Yuxin
    Chekshin, Nikita
    Yu, Jin-Quan
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2022, 144 (11) : 4727 - 4733
  • [4] Palladium-Catalyzed β-C(sp3)-H Arylation of Aliphatic Ketones Enabled by a Transient Directing Group
    Wang, Yangyang
    Wu, Gaorong
    Xu, Xiaobo
    Pang, Binghan
    Liao, Shaowen
    Ji, Yafei
    JOURNAL OF ORGANIC CHEMISTRY, 2021, 86 (10): : 7296 - 7303
  • [5] Ligand-Enabled PdII-Catalyzed Iterative γ-C(sp3)-H Arylation of Free Aliphatic Acid
    Dolui, Pravas
    Das, Jayabrata
    Chandrashekar, Hediyala B.
    Anjana, S. S.
    Maiti, Debabrata
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2019, 58 (39) : 13773 - 13777
  • [6] Transient Directing Groups for the Most Straightforward Arylation of C(sp3)-H Bonds
    Kumada, Kanako
    JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN, 2019, 77 (01) : 69 - 70
  • [7] PdII-Catalyzed Intermolecular Amination of Unactivated C(sp3)H Bonds
    Gou, Quan
    Liu, Gang
    Liu, Zi-Ning
    Qin, Jun
    CHEMISTRY-A EUROPEAN JOURNAL, 2015, 21 (44) : 15491 - 15495
  • [8] Methylene C(sp3)-H Arylation of Aliphatic Ketones Using a Transient Directing Group
    Hong, Kai
    Park, Hojoon
    Yu, Jin-Quan
    ACS CATALYSIS, 2017, 7 (10): : 6938 - 6941
  • [9] PdII-Catalyzed C(alkenyl)-H Activation Facilitated by a Transient Directing Group
    Liu, Mingyu
    Sun, Juntao
    Erbay, Tugce G.
    Ni, Hui-Qi
    Martin-Montero, Raul
    Liu, Peng
    Engle, Keary M.
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2022, 61 (25)
  • [10] Nano palladium catalyzed C(sp3)-H bonds arylation by a transient directing strategy
    Chen, Jianxia
    Bai, Chaolumen
    Ma, Hongpeng
    Liu, Dan
    Bao, Yong-Sheng
    CHINESE CHEMICAL LETTERS, 2021, 32 (01) : 465 - 469
12345