Ligand-Enabled γ-C(sp3)-H Activation of Ketones

被引：121
|
作者：
Zhu, Ru-Yi [1 ]
Li, Zi-Qi [1 ]
Park, Han Seul [1 ]
Senanayake, Chris H. [2 ]
Yu, Jin-Quan [1 ]
机构：
[1] Scripps Res Inst, Dept Chem, 10550 N Torrey Pines Rd, La Jolla, CA 92037 USA
[2] Boehringer Ingelheim Pharmaceut Inc, Dept Chem Dev, 900 Ridgebury Rd, Ridgefield, CT 06877 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 10期
关键词：
C-H BONDS; CATALYZED INTRAMOLECULAR AMINATION; INTERMOLECULAR AMIDATION; C(SP(3))-H ARYLATION; PALLADIUM; FUNCTIONALIZATION; GAMMA;
D O I：
10.1021/jacs.8b01359
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
We report the first example of Pd(II)-catalyzed gamma-C(sp(3))-H activation of ketones directed by a practical 2,2-dimethyl aminooxyacetic acid auxiliary. 2-Pyridone ligands are identified to enable C(sp(3))-H activation for the first time. A rare six-membered palladacycle intermediate is isolated and characterized to elucidate the reaction mechanism. Both (hetero)arylation and vinylation of gamma-C(sp(3))-H bonds are demonstrated. Sequential beta- and gamma-C(sp(3))-H (hetero)arylation of muscone showcases the utility of this method for late-stage diversification. A convenient Mn(II)-catalyzed auxiliary removal is also developed to further underscore the practicality of this transformation.
引用
收藏
页码：3564 / 3568
页数：5
相关论文
共 50 条
  • [31] Highly Versatile β-C(sp3)-H Iodination of Ketones Using a Practical Auxiliary
    Zhu, Ru-Yi
    Liu, Luo-Yan
    Yu, Jin-Quan
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (36) : 12394 - 12397
  • [32] Ligand Enabled Pd(II)-Catalyzed γ-C(sp3)-H Lactamization of Native Amides
    Liu, Shuang
    Zhuang, Zhe
    Qiao, Jennifer X.
    Yeung, Kap-Sun
    Su, Shun
    Cherney, Emily C.
    Ruan, Zheming
    Ewing, William R.
    Poss, Michael A.
    Yu, Jin-Quan
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2021, 143 (51) : 21657 - 21666
  • [33] Ligand-Enabled Stereoselective β-C(sp3)-H Fluorination: Synthesis of Unnatural Enantiopure anti-β-Fluoro-α-amino Acids
    Zhu, Ru-Yi
    Tanaka, Keita
    Li, Gen-Cheng
    He, Jian
    Fu, Hai-Yan
    Li, Su-Hua
    Yu, Jin-Quan
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (22) : 7067 - 7070
  • [34] 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
  • [35] Ligand-enabled meta-C-H activation using a transient mediator
    Wang, Xiao-Chen
    Gong, Wei
    Fang, Li-Zhen
    Zhu, Ru-Yi
    Li, Suhua
    Engle, Keary M.
    Yu, Jin-Quan
    NATURE, 2015, 519 (7543) : 334 - 338
  • [36] Palladium-Catalyzed β-C(sp3)-H Nitrooxylation of Ketones and Amides Using Practical Oxidants
    Xue, Yuan
    Park, Han Seul
    Jiang, Chao
    Yu, Jin-Quan
    ACS CATALYSIS, 2021, 11 (22) : 14188 - 14193
  • [37] A Catalytic Alkylation of Ketones via sp3 C-H Bond Activation
    Peng, Xue
    Hirao, Yuki
    Yabu, Shunsuke
    Sato, Hirofumi
    Higashi, Masahiro
    Akai, Takuya
    Masaoka, Shigeyuki
    Mitsunuma, Harunobu
    Kanai, Motomu
    JOURNAL OF ORGANIC CHEMISTRY, 2023, 88 (10) : 6333 - 6346
  • [38] Synthesis of β-(Hetero)aryl Ketones via Ligand-Enabled Nondirected C-H Alkylation
    Bairagi, Yogesh
    Porey, Sandip
    Vummaleti, Sai V. C.
    Zhang, Xinglong
    Lahiri, Goutam Kumar
    Maiti, Debabrata
    ACS CATALYSIS, 2024, 14 (20): : 15654 - 15664
  • [39] Post-Assembly Modification of Peptides by Ligand-Enabled β-C(sp3)-H Arylation of Alanine at the C-Terminus: Overcoming the Inhibition Effect of Peptide Bonds
    Li, Ming
    Akintelu, Sunday A.
    Yao, Bo
    ORGANIC LETTERS, 2021, 23 (12) : 4807 - 4812
  • [40] Direct C(sp3)-H Activation of Carboxylic Acids
    Uttry, Alexander
    van Gemmeren, Manuel
    SYNTHESIS-STUTTGART, 2020, 52 (04): : 479 - 488
12345