Computational study of silver-catalyzed stereoselective hydroalkylation of alkynes: Pauli repulsion controlled Z/E selectivity

被引：24
作者：
Hu, Lingfei [1 ]
Gao, Han [1 ]
Hu, Yanlei [1 ]
Lv, Xiangying [1 ]
Wu, Yan-Bo [2 ,3 ]
Lu, Gang [1 ]
机构：
[1] Shandong Univ, Sch Chem & Chem Engn, Key Lab Colloid & Interface Chem, Minist Educ, Jinan 250100, Shandong, Peoples R China
[2] Shanxi Univ, Inst Mol Sci, Key Lab Mat Energy Convers & Storage Shanxi Prov, Taiyuan 030006, Shanxi, Peoples R China
[3] Shanxi Univ, Inst Mol Sci, Minist Educ, Key Lab Chem Biol & Mol Engn, Taiyuan 030006, Shanxi, Peoples R China
来源：
CHEMICAL COMMUNICATIONS | 2021年 / 57卷 / 52期
基金：
中国国家自然科学基金;
关键词：
TERMINAL ALKYNES; CARBOXYLATION; ORIGIN; MODEL;
D O I：
10.1039/d1cc01917a
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The mechanism and origin of stereoselectivity of silver-catalyzed hydroalkylation of alkynes were computationally investigated at the B3LYP-D3BJ/6-311+G(d,p)-SDD//B3LYP/6-31G(d)-LANL2DZ level. The complex of alkynyl trialkylboronate with cationic silver is a key intermediate, which triggers the rate- and stereoselectivity-determining 1,2-migration step. Energy decomposition analysis indicates that the difference of Pauli repulsion dominates the stereoselectivity.
引用
收藏
页码：6412 / 6415
页数：4
相关论文
共 43 条
  • [1] Diastereodivergent Reductive Cross Coupling of Alkynes through Tandem Catalysis: Z- and E-Selective Hydroarylation of Terminal Alkynes
    Armstrong, Megan K.
    Goodstein, Madison B.
    Lalic, Gojko
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2018, 140 (32) : 10233 - 10241
  • [2] Difunctionalization of C-C σ-Bonds Enabled by the Reaction of Bicyclo[1.1.0]butyl Boronate Complexes with Electrophiles: Reaction Development, Scope, and Stereochemical Origins
    Bennett, Steven H.
    Fawcett, Alexander
    Denton, Elliott H.
    Biberger, Tobias
    Fasano, Valerio
    Winter, Nils
    Aggarwal, Varinder K.
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2020, 142 (39) : 16766 - 16775
  • [3] Analyzing Reaction Rates with the Distortion/Interaction-Activation Strain Model
    Bickelhaupt, F. Matthias
    Houk, Kendall N.
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (34) : 10070 - 10086
  • [4] AgN3-Catalyzed Hydroazidation of Terminal Alkynes and Mechanistic Studies
    Cao, Shanshan
    Ji, Qinghe
    Li, Huaizhi
    Pang, Maolin
    Yuan, Haiyan
    Zhang, Jingping
    Bi, Xihe
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2020, 142 (15) : 7083 - 7091
  • [5] Z-Selective Olefin Synthesis via Iron-Catalyzed Reductive Coupling of Alkyl Halides with Terminal Arylalkynes
    Cheung, Chi Wai
    Zhurkin, Fedor E.
    Hu, Xile
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (15) : 4932 - 4935
  • [6] Nickel-Catalyzed Enantioselective Conjunctive Cross-Coupling of 9-BBN Borates
    Chierchia, Matteo
    Law, Chunyin
    Morken, James P.
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (39) : 11870 - 11874
  • [7] Preparation of substituted enol derivatives from terminal alkynes and their synthetic utility
    DeBergh, John R.
    Spivey, Kathleen M.
    Ready, Joseph M.
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (25) : 7828 - +
  • [8] Strain-Release-Driven Homologation of Boronic Esters: Application to the Modular Synthesis of Azetidines
    Fawcett, Alexander
    Murtaza, Amna
    Gregson, Charlotte H. U.
    Aggarwal, Varinder K.
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2019, 141 (11) : 4573 - 4578
  • [9] Carbopalladation of C-C σ-bonds enabled by strained boronate complexes
    Fawcett, Alexander
    Biberger, Tobias
    Aggarwal, Varinder K.
    [J]. NATURE CHEMISTRY, 2019, 11 (02) : 117 - 122
  • [10] The activation strain model and molecular orbital theory: understanding and designing chemical reactions
    Fernandez, Israel
    Bickelhaupt, F. Matthias
    [J]. CHEMICAL SOCIETY REVIEWS, 2014, 43 (14) : 4953 - 4967
12345