A syn outer-sphere oxidative addition: the reaction mechanism in Pd/Senphos-catalyzed carboboration of 1,3-enynes

被引：13
|
作者：
Wang, Ziyong [1 ]
Lamine, Walid [2 ]
Miqueu, Karinne [2 ]
Liu, Shih-Yuan [1 ,2 ]
机构：
[1] Boston Coll, Dept Chem, Chestnut Hill, MA 02467 USA
[2] Univ Pau & Pays Adour, E2S UPPA CNRS, Inst Sci Analyt & Physicochim Environm & Mat IPREM, Helioparc,2 Ave P Angot, F-64053 Pau 09, France
来源：
CHEMICAL SCIENCE | 2023年 / 14卷 / 08期
基金：
美国国家卫生研究院;
关键词：
ALKENYL BORONIC ACIDS; STEREOSELECTIVE-SYNTHESIS; EFFICIENT METHOD; RECENT PROGRESS; ALKYNES; TAMOXIFEN; ALKYNYLBORATION; OLEFINS; BOND; ARYL;
D O I：
10.1039/d2sc05828f
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
We report a combined experimental and computational study of Pd/Senphos-catalyzed carboboration of 1,3-enynes utilizing DFT calculations, P-31 NMR study, kinetic study, Hammett analysis and Arrhenius/Eyring analysis. Our mechanistic study provides evidence against the conventional inner-sphere beta-migratory insertion mechanism. Instead, a syn outer-sphere oxidative addition mechanism featuring a Pd-pi-allyl intermediate followed by coordination-assisted rearrangements is consistent with all the experimental observations.
引用
收藏
页码：2082 / 2090
页数：9
相关论文
共 50 条
  • [1] Mechanism of Pd/Senphos-Catalyzed trans-Hydroboration of 1,3-Enynes: Experimental and Computational Evidence in Support of the Unusual Outer-Sphere Oxidative Addition Pathway
    Zhang, Yuanzhe
    Wang, Ziyong
    Lamine, Walid
    Xu, Senmiao
    Li, Bo
    Chrostowska, Anna
    Miqueu, Karinne
    Liu, Shih-Yuan
    JOURNAL OF ORGANIC CHEMISTRY, 2023, 88 (04): : 2415 - 2424
  • [2] Pd-Senphos Catalyzedtrans-Selective Cyanoboration of 1,3-Enynes
    Zhang, Yuanzhe
    Li, Bo
    Liu, Shih-Yuan
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2020, 59 (37) : 15928 - 15932
  • [3] C-Boron Enolates Enable Palladium Catalyzed Carboboration of Internal 1,3-Enynes
    Wang, Ziyong
    Wu, Jason
    Lamine, Walid
    Li, Bo
    Sotiropoulos, Jean-Marc
    Chrostowska, Anna
    Miqueu, Karinne
    Liu, Shih-Yuan
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2021, 60 (39) : 21231 - 21236
  • [4] Rhodium-Catalyzed Dimerization of Arylacetylenes and Addition of Malonates to 1,3-Enynes
    Mochizuki, Katsufumi
    Sakai, Kazunori
    Kochi, Takuya
    Kakiuchi, Fumitoshi
    SYNTHESIS-STUTTGART, 2013, 45 (15): : 2088 - 2092
  • [5] Gold Catalyzed [3+2] Oxidative Annulation of 1,3-Enynes with Indoles
    Zou, Qiang
    Wang, Yu-Jiang
    Wan, Ya-Ru
    Chen, Zili
    ASIAN JOURNAL OF ORGANIC CHEMISTRY, 2024, 13 (12)
  • [6] Direct access to spirocycles by Pd/WingPhos-catalyzed enantioselective cycloaddition of 1,3-enynes
    Li, Long
    Wang, Shan
    Luo, Pengfei
    Wang, Ran
    Wang, Zheng
    Li, Xiaoguang
    Deng, Yuhua
    Peng, Fangzhi
    Shao, Zhihui
    NATURE COMMUNICATIONS, 2021, 12 (01)
  • [7] Direct access to spirocycles by Pd/WingPhos-catalyzed enantioselective cycloaddition of 1,3-enynes
    Long Li
    Shan Wang
    Pengfei Luo
    Ran Wang
    Zheng Wang
    Xiaoguang Li
    Yuhua Deng
    Fangzhi Peng
    Zhihui Shao
    Nature Communications, 12
  • [8] Pd-catalyzed functionalization of 1,3-enynes via alkylene-x-allylpalladium intermediates
    Li, Long
    Wang, Shan
    Jakhar, Ajay
    Shao, Zhihui
    GREEN SYNTHESIS AND CATALYSIS, 2023, 4 (02): : 124 - 134
  • [9] Stereoselective Access to (E)-1,3-Enynes through Pd/Cu-Catalyzed Alkyne Hydrocarbation of Allenes
    Jeanne-Julien, Louis
    Masson, Guillaume
    Kouoi, Remy
    Regazzetti, Anne
    Genta-Jouve, Gregory
    Gandon, Vincent
    Roulland, Emmanuel
    ORGANIC LETTERS, 2019, 21 (09) : 3136 - 3141
  • [10] Copper/Photoredox-Catalyzed Regioselective 1,4-Addition to 1,3-Enynes: A Convenient Access to Perfluoroalkylated Allenes
    Chen, Ya
    Wang, Quanyuan
    Peng, Keyi
    Cheng, Lilei
    She, Ziyi
    Deng, Guo-Jun
    CHINESE JOURNAL OF CHEMISTRY, 2024, 42 (17) : 2023 - 2028
12345