Net Oxidative Addition of C(sp3)-F Bonds to Iridium via Initial C-H Bond Activation

被引:145
|
作者
Choi, Jongwook [1 ]
Wang, David Y. [1 ]
Kundu, Sabuj [1 ]
Choliy, Yuriy [1 ]
Emge, Thomas J. [1 ]
Krogh-Jespersen, Karsten [1 ]
Goldman, Alan S. [1 ]
机构
[1] Rutgers State Univ, Dept Chem & Chem Biol, New Brunswick, NJ 08903 USA
关键词
TRANSITION-METAL-COMPLEXES; REDUCTIVE ELIMINATION; FLUORINE; REACTIVITY; CHEMISTRY; MECHANISM; HYDROGEN;
D O I
10.1126/science.1200514
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
Carbon-fluorine bonds are the strongest known single bonds to carbon and as a consequence can prove very hard to cleave. Alhough vinyl and aryl C-F bonds can undergo oxidative addition to transition metal complexes, this reaction has appeared inoperable with aliphatic substrates. We report the addition of C(sp(3))-F bonds (including alkyl-F) to an iridium center via the initial, reversible cleavage of a C-H bond. These results suggest a distinct strategy for the development of catalysts and promoters to make and break C-F bonds, which are of strong interest in the context of both pharmaceutical and environmental chemistry.
引用
收藏
页码:1545 / 1548
页数:4
相关论文
共 50 条
  • [1] Cleavage of sp3 C-O Bonds via Oxidative Addition of C-H Bonds
    Choi, Jongwook
    Choliy, Yuriy
    Zhang, Xiawei
    Emge, Thomas J.
    Krogh-Jespersen, Karsten
    Goldman, Alan S.
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (43) : 15627 - +
  • [2] Metal-free oxidative C-C bond formation of active methylenic sp3 C-H bonds with benzylic sp3 C-H and allylic sp3 C-H bonds mediated by DDQ
    Ramesh, D.
    Ramulu, U.
    Rajaram, S.
    Prabhakar, P.
    Venkateswarlu, Y.
    TETRAHEDRON LETTERS, 2010, 51 (37) : 4898 - 4903
  • [3] Oxidative addition and cleavage of sp3 C-F Bond by pincer iridium complexes
    Choi, Jongwook
    Goldman, Alan S.
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2010, 240
  • [4] Palladium-Catalyzed Oxidative Carbonylation of Benzylic C-H Bonds via Nondirected C(sp3)-H Activation
    Xie, Pan
    Xie, Yinjun
    Qian, Bo
    Zhou, Han
    Xia, Chungu
    Huang, Hanmin
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (24) : 9902 - 9905
  • [5] Palladium(ii)-catalyzed oxidative C(sp3)-P bond formation via C(sp3)-H bond activation
    Chen, Lijin
    Zhou, Zhenfei
    Zhang, Saifei
    Li, Xiaoqian
    Ma, Xuebing
    Dong, Jiaxing
    CHEMICAL COMMUNICATIONS, 2019, 55 (91) : 13693 - 13696
  • [6] 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
  • [7] Enantioselective synthesis of γ-amino acid derivatives via iridium catalyzed activation of sp3 C-H bond
    Tahara, Yuki
    Michino, Masamichi
    Ito, Mamoru
    Shibata, Takanori
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2015, 250
  • [8] Copper-Catalyzed Direct Trifluoromethylthiolation of Benzylic C-H Bonds via Nondirected Oxidative C(sp3)-H Activation
    Chen, Chao
    Xu, Xiu-Hua
    Yang, Bin
    Qing, Feng-Ling
    ORGANIC LETTERS, 2014, 16 (12) : 3372 - 3375
  • [9] C-H Bond Activation and Subsequent C(sp2)-C(sp3) Bond Formation: Coupling of Bromomethyl and Triphenylphosphine in an Iridium Complex
    Lin, Yumei
    Xu, Hui
    Gong, Lei
    Wen, Ting Bin
    He, Xu-Min
    Xia, Haiping
    ORGANOMETALLICS, 2010, 29 (13) : 2904 - 2910
  • [10] Selective activation of Sp3 C-H bonds of tertiary amines
    Lu, CC
    Peters, JC
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2002, 224 : U728 - U728