Mechanism of Nakamura's Bisphosphine-Iron-Catalyzed Asymmetric C(sp2)-C(sp3) Cross-Coupling Reaction: The Role of Spin in Controlling Arylation Pathways

被引：59
|
作者：
Lee, Wes [1 ]
Zhou, Jun [1 ]
Gutierrez, Osvaldo [1 ]
机构：
[1] Univ Maryland, Dept Chem & Biochem, College Pk, MD 20742 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2017年 / 139卷 / 45期
关键词：
DENSITY-FUNCTIONAL THEORY; ARYL-GRIGNARD-REAGENTS; ALKYL-HALIDES; ALKENYL HALIDES; KUMADA; THERMOCHEMISTRY; NUCLEOPHILES; DERIVATIVES; COMPLEX; FERRATE;
D O I：
10.1021/jacs.7b06377
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Quantum mechanical calculations are employed to investigate the mechanism and origin of stereoinduction in asymmetric iron-catalyzed C(sp(2))-C(sp(3)) cross-coupling reaction between Grignard reagents and alpha-chloroesters. A coherent mechanistic picture of this transformation is revealed. These results have broad implications for understanding the mechanisms of iron-catalyzed cross-coupling reactions and rational design of novel iron-based catalysts for asymmetric transformations.
引用
收藏
页码：16126 / 16133
页数：8
相关论文
共 50 条
  • [41] Stereoselective Synthesis of C -Aryl-α-Glycosides by Reductive C(sp 2 )-C(sp 3 ) Cross-Coupling Reaction
    Kudo, Noyuri
    Chiba, Suzuka
    Ono, Shunsuke
    Nagatoishi, Masataka
    Yoritate, Makoto
    Karasawa, Satoru
    Usui, Kazuteru
    Hirai, Go
    SYNLETT, 2025, 36 (04) : 357 - 362
  • [42] Mechanisms, challenges, and opportunities of dual Ni/photoredox-catalyzed C(sp2)-C(sp3) cross-couplings
    Yuan, Mingbin
    Gutierrez, Osvaldo
    WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE, 2022, 12 (03)
  • [43] Visible-light-driven photoredox-catalyzed C(sp3)-C(sp3) cross-coupling of N-arylamines with cycloketone oxime esters
    Zhou, Sheng-Yun
    Zhang, Ding
    Liu, Xiao-Jie
    Qin, Jing-Hao
    Fu, Zheng-Li
    Li, Shuang-Long
    Cai, Fang-Jun
    Li, Yang
    Li, Jin-Heng
    ORGANIC CHEMISTRY FRONTIERS, 2022, 9 (09): : 2534 - 2540
  • [44] Iridium-Catalyzed Stereocontrolled C(sp3)-C(sp3) Cross-Coupling of Boronic Esters and Allylic Carbonates Enabled by Boron-to-Zinc Transmetalation
    Shen, Hong-Cheng
    Aggarwal, Varinder K.
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2025, 147 (07) : 5583 - 5589
  • [45] General C(sp2)-C(sp3) Cross-Electrophile Coupling Reactions Enabled by Overcharge Protection of Homogeneous Electrocatalysts
    Truesdell, Blaise L.
    Hamby, Taylor B.
    Sevov, Christo S.
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2020, 142 (12) : 5884 - 5893
  • [46] Palladium-Catalyzed (3+2) Annulation of Aromatic Acids by C(sp3)-H Olefination and Decarboxylative Cross-Coupling Reaction
    Xu, Xiaobo
    Wang, Yangyang
    Yu, Xiao
    Liu, Xian
    Hao, Liqiang
    Ji, Yafei
    ORGANIC LETTERS, 2024, 26 (07) : 1338 - 1342
  • [47] Palladium-catalyzed C(sp3)-Si cross-coupling silylation of benzyl halides with hydrosilanes
    Zhou, Xiao-Hua
    Zhu, Jun-Hui
    Song, Guang-Ao
    Jiang, Xin-Li
    Fang, Xiao-Jun
    Xu, Zheng
    Xu, Li-Wen
    ORGANIC CHEMISTRY FRONTIERS, 2023, 10 (21) : 5443 - 5450
  • [48] Bu4NI-catalyzed, oxidative C(sp2)-C(sp3)cross dehydrogenative coupling for the regioselective direct C-3 benzylation of 2H-indazoles
    Yadav, Lalit
    Chaudhary, Sandeep
    ORGANIC & BIOMOLECULAR CHEMISTRY, 2020, 18 (30) : 5927 - 5936
  • [49] CU2O-Catalyzed C(SP3)-H/C(SP3)-H Cross-Coupling Using TEMPO: Synthesis of 3-(2-Oxoalkyl)-3-hydroxyoxindoles
    Wang, Baoshuang
    Zhu, Jiayi
    Wei, Yang
    Luo, Guotian
    Qu, Hongen
    Liu, Liang-Xian
    SYNTHETIC COMMUNICATIONS, 2015, 45 (24) : 2841 - 2848
  • [50] Iron-catalysed tandem cross-dehydrogenative coupling (CDC) of terminal allylic C(sp3) to C(sp2) of styrene and benzoannulation in the synthesis of polysubstituted naphthalenes
    Liu, Hua
    Cao, Li
    Sun, Jia
    Fossey, John S.
    Deng, Wei-Ping
    CHEMICAL COMMUNICATIONS, 2012, 48 (21) : 2674 - 2676
12345