Theoretical Analysis of a Three-Component Reaction between Two Diazo Compounds and a Hydroxylamine Derivative: Mechanism, Enantioselectivity, and Effect of Cooperative Catalysis

被引:4
|
作者
Qi, Simeng [1 ]
Ma, Ji [1 ]
Yan, Guowei [1 ]
Kirillov, Alexander M. [2 ]
Yang, Lizi [3 ]
Fang, Ran [1 ]
机构
[1] Shaanxi Univ Sci & Technol, Coll Chem & Chem Engn, Key Lab Chem Addit China Natl Light Ind, Xian 710021, Peoples R China
[2] Univ Lisbon, Dept Engn Quim, Inst Super Tecn, Ctr Quim Estrutural,Inst Mol Sci, P-1049001 Lisbon, Portugal
[3] Lanzhou Univ, Coll Chem & Chem Engn, Lanzhou 730000, Peoples R China
来源
JOURNAL OF ORGANIC CHEMISTRY | 2023年 / 88卷 / 24期
基金
中国国家自然科学基金;
关键词
EFFECTIVE CORE POTENTIALS; O-H INSERTION; MOLECULAR CALCULATIONS; C-H; DENSITY FUNCTIONALS; BASIS-SETS; ACTIVATION; ENERGY; ENERGETICS; DISTORTION;
D O I
10.1021/acs.joc.3c02061
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The mechanism, enantioselectivity, and effect of chiral phosphoric acid (CPA) cocatalyst were investigated by the density functional theory (DFT) for the three-component asymmetric aminohydroxylation between two diazo compounds and a hydroxylamine derivative. This type of cascade process is cooperatively catalyzed by Rh-2(OAc)(4) and CPA. The obtained results clearly indicate that the first step of the global reaction involves a nucleophilic attack at the nitrogen center of N-hydroxyaniline by rhodium-carbene intermediates producing imines. Subsequently, an enolate intermediate was recognized as the key species generated from the second diazo compound and the leaving benzyl alcohol (BnOH) fragment of the first step and in the presence of the same dirhodium catalyst. Then, the reaction is terminated by the asymmetric Mannich-type addition, delivering the aminohydroxylation products of an S-R conformation with the assistance of chiral phosphoric acid. The distortion/interaction analysis shows that the relative distortions of CPA and the enol play a vital role in the energy ordering of the stereocontrolling transition states (TSs). Furthermore, the influence of different substituents in CPA was fully rationalized by distortion/interaction analysis. This study opens up novel synthetic possibilities and improves the reaction predictability when exploring the related types of cooperatively catalyzed organic transformations.
引用
收藏
页码:17215 / 17226
页数:12
相关论文
共 35 条
  • [21] A gold(i)-catalysed chemoselective three-component reaction between phenols, α-diazocarbonyl compounds and allenamides
    Yu, Sifan
    Chen, Jinzhou
    Liu, Gengxin
    Lei, Jinping
    Hu, Wenhao
    Qiu, Huang
    CHEMICAL COMMUNICATIONS, 2020, 56 (11) : 1649 - 1652
  • [22] Hydrocyanative Cyclization and Three-Component Cross-Coupling Reaction between Allenes and Alkynes under Nickel Catalysis
    Arai, Shigeru
    Amako, Yuka
    Yang, Xiaofei
    Nishida, Atsushi
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (31) : 8147 - 8150
  • [23] Three-component coupling reaction for the synthesis of fully substituted triazoles: reactivity control of Cu-acetylide toward alkyl azides and diazo compounds
    Chen, Fa-Jie
    Mamidipalli, Phani
    Sabbasani, Venkata Reddy
    Liu, Huaqing
    Xia, Yuanzhi
    Lee, Daesung
    ORGANIC CHEMISTRY FRONTIERS, 2021, 8 (21) : 6095 - 6107
  • [24] Synthesis of γ-Sulfur-Substituted Ketones via Rh(II)/Sc(III) a Cocatalyzed Three-Component Reaction of Diazo Compounds with Thiophenols and Enones
    Xiao, Guolan
    Ma, Chaoqun
    Wu, Xiang
    Xing, Dong
    Hu, Wenhao
    JOURNAL OF ORGANIC CHEMISTRY, 2018, 83 (08): : 4786 - 4791
  • [25] Theoretical study of the reaction-diffusion model of a three-component photopolymerizable system taking into account the shrinking effect
    Bielykh, S. P.
    Galstian, T. V.
    Reshetnyak, V. Yu.
    RESULTS IN OPTICS, 2023, 11
  • [26] Radical-Triggered Three-Component Coupling Reaction of Alkenylboronates, α-Halocarbonyl Compounds, and Organolithium Reagents: The Inverse Ylid Mechanism
    Tappin, Nicholas D. C.
    Gnagi-Lux, Manuel
    Renaud, Philippe
    CHEMISTRY-A EUROPEAN JOURNAL, 2018, 24 (44) : 11498 - 11502
  • [27] One-pot three-component tandem reaction of diazo compounds with anilines and unsaturated ketoesters: a novel synthesis of 2,3-dihydropyrrole derivatives
    Zhu, Yingguang
    Zhai, Changwei
    Yue, Yongli
    Yang, Liping
    Hu, Wenhao
    CHEMICAL COMMUNICATIONS, 2009, (11) : 1362 - 1364
  • [28] Three-component reaction between substituted β-nitrostyrenes, β-dicarbonyl compounds and amines: diversity-oriented synthesis of novel β-enaminones
    Ye, Weijian
    Li, Yan
    Zhou, Lanxiang
    Liu, Juanjuan
    Wang, Cunde
    GREEN CHEMISTRY, 2015, 17 (01) : 188 - 192
  • [29] Enantioselective Synthesis of α-Mercapto-β-amino Esters via Rh(II)/Chiral Phosphoric Acid-Cocatalyzed Three-Component Reaction of Diazo Compounds, Thiols, and Imines
    Xiao, Guolan
    Ma, Chaoqun
    Xing, Dong
    Hu, Wenhao
    ORGANIC LETTERS, 2016, 18 (23) : 6086 - 6089
  • [30] Retrospective comparison between a two- and three-component ankle arthroplasty: clinical and functional evaluation via gait analysis
    Lullini, Giada
    Caravaggi, Paolo
    Leardini, Alberto
    Ortolani, Maurizio
    Mazzotti, Antonio
    Giannini, Sandro
    Berti, Lisa
    CLINICAL BIOMECHANICS, 2020, 80