Computational study on the Rh-catalyzed C-C activation of cyclopropanol to construct diketone or monoketone

被引:0
作者
Liu, Tao [1 ,2 ]
Wang, Ping [2 ]
Ren, Hong [3 ]
机构
[1] Jining Univ, Dept Chem & Chem Engn, Qufu 273155, Shandong, Peoples R China
[2] Qufu Normal Univ, Sch Chem & Chem Engn, Qufu, Shandong, Peoples R China
[3] Jining Univ, Informat Management Ctr, Qufu, Shandong, Peoples R China
基金
中国国家自然科学基金;
关键词
1,6-diketone; beta-hydride elimination; DFT; selectivity; GAS-PHASE ENTROPIES; H ACTIVATION; MECHANISM; SOLVENT; REGIOSELECTIVITY; SOLVATION; OXIDATION; IMPACT; DFT;
D O I
10.1002/qua.26438
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
The mechanisms of C-C activation of 1-benzylcyclopropan-1-ol to produce 1,6-diketone have been investigated by density functional theory calculations. The catalyst [Cp*RhCl2](2) and additive Ag2CO3 play an important role in controlling the selectivity. By using [Cp*RhCl2](2) as the catalyst and Ag2CO3 as the additive, the product is 1,6-diketone, whereas the beta-hydride elimination product could not be obtained. The product would become monoketone in the absence of [Cp*RhCl2](2). In addition, the combination of catalyst [Cp*RhCl2](2) and additive AgOAc would also lead to monoketone. The observed selectivity could be attributed to the electronic effect.
引用
收藏
页数:7
相关论文
共 45 条
  • [2] Aqueous Acidities of Primary Benzenesulfonamides: Quantum Chemical Predictions Based on Density Functional Theory and SMD
    Aidas, Kesstutis
    Lanevskij, Kiril
    Kubilius, Rytis
    Juska, Liutauras
    Petkevicius, Daumantas
    Japertas, Pranas
    [J]. JOURNAL OF COMPUTATIONAL CHEMISTRY, 2015, 36 (29) : 2158 - 2167
  • [3] ENERGY-ADJUSTED ABINITIO PSEUDOPOTENTIALS FOR THE 2ND AND 3RD ROW TRANSITION-ELEMENTS
    ANDRAE, D
    HAUSSERMANN, U
    DOLG, M
    STOLL, H
    PREUSS, H
    [J]. THEORETICA CHIMICA ACTA, 1990, 77 (02): : 123 - 141
  • [4] Umpolung α-Silylation of Cyclopropyl Acetates via Low-Temperature Catalytic C-C Activation
    Avullala, Thirupataiah
    Asgari, Parham
    Hua, Yuanda
    Bokka, Apparao
    Ridlen, Shawn G.
    Yum, Kyungsuk
    Dias, H. V. Rasika
    Jeon, Junha
    [J]. ACS CATALYSIS, 2019, 9 (01) : 402 - 408
  • [5] Specific-Ion Effects on the Aggregation Mechanisms and Protein-Protein Interactions for Anti-streptavidin Immunoglobulin Gamma-1
    Barnett, Gregory V.
    Razinkov, Vladimir I.
    Kerwin, Bruce A.
    Laue, Thomas M.
    Woodka, Andrea H.
    Butler, Paul D.
    Perevozchikova, Tatiana
    Roberts, Christopher J.
    [J]. JOURNAL OF PHYSICAL CHEMISTRY B, 2015, 119 (18) : 5793 - 5804
  • [6] Multiple roles of silver salts in palladium-catalyzed C-H activations
    Bay, Katherine L.
    Yang, Yun-Fang
    Houk, K. N.
    [J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2018, 864 : 19 - 25
  • [7] Theoretical characterization of the "very rapid" Mo(V) species generated in the oxidation of xanthine oxidase
    Bayse, CA
    [J]. INORGANIC CHEMISTRY, 2006, 45 (05) : 2199 - 2202
  • [9] Are Solvent and Dispersion Effects Crucial in Olefin Polymerization DFT Calculations? Some Insights from Propylene Coordination and Insertion Reactions with Group 3 and 4 Metallocenes
    Castro, Ludovic
    Kirillov, Evgueni
    Miserque, Olivier
    Welle, Alexandre
    Haspeslagh, Luc
    Carpentier, Jean-Francois
    Maron, Laurent
    [J]. ACS CATALYSIS, 2015, 5 (01): : 416 - 425
  • [10] Mechanism and control of rare tautomer trapping at a metal-metal bond: Adenine binding to dirhodium antitumor agents
    Deubel, Dirk V.
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (02) : 665 - 675