Double allylic defluorinative alkylation of 1,1-bisnucleophiles with (trifluoromethyl)alkenes: construction of all-carbon quaternary centers

被引：44
|
作者：
Cai, Yingying [1 ]
Zeng, Hao [1 ]
Zhu, Chuanle [1 ]
Liu, Chi [1 ]
Liu, Guangying [1 ]
Jiang, Huanfeng [1 ]
机构：
[1] South China Univ Technol, Sch Chem & Chem Engn, Key Lab Funct Mol Engn Guangdong Prov, Guangzhou 510610, Peoples R China
来源：
ORGANIC CHEMISTRY FRONTIERS | 2020年 / 7卷 / 10期
基金：
中国国家自然科学基金;
关键词：
F BOND ACTIVATION; GEM-DIFLUOROALKENES; DIAZO-COMPOUNDS; FLUORINE; SUBSTITUTION; NITRILE; DIFLUOROOLEFINATION; PHARMACEUTICALS; CATALYSIS; TERTIARY;
D O I：
10.1039/d0qo00121j
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
A double allylic defluorinative alkylation reaction of 1,1-bisnucleophiles with (trifluoromethyl)alkenes is reported that occurs via the exclusively regioselective S(N)2 reaction. Various aliphatic nitriles, esters, and indolin-2-one derivatives could serve as 1,1-bisnucleophiles, delivering diverse attractive symmetric gem-difluoroalkene substituted products in high yields via the construction of all-carbon quaternary centers. Interestingly, the chemoselective SNV reaction between gem-difluoroalkenes and nucleophiles is completely inhibited. The nitrile group might help to stabilize the alpha-carbanion intermediates.
引用
收藏
页码：1260 / 1265
页数：6
相关论文
共 50 条
  • [21] Diastereoselective construction of continuous all-carbon quaternary centers via intramolecular oxidative coupling reaction
    Xie, Weiqing
    Wang, Hexiang
    Fan, Feng
    Tian, Junshan
    Zuo, Zhiwei
    Zi, Weiwei
    Gao, Kun
    Ma, Dawei
    TETRAHEDRON LETTERS, 2013, 54 (33) : 4392 - 4396
  • [22] Construction of Quaternary Stereogenic Carbon Centers through Copper-Catalyzed Enantioselective Allylic Alkylation of Azoles
    Ohmiya, Hirohisa
    Zhang, Heng
    Shibata, Saori
    Harada, Ayumi
    Sawamura, Masaya
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (15) : 4777 - 4780
  • [23] Enantioselective construction of all-carbon quaternary spirocenters through a Pd-catalyzed asymmetric intramolecular ipso-Friedel-Crafts allylic alkylation of phenols
    Yoshida, Mariko
    Nemoto, Tetsuhiro
    Zhao, Zengduo
    Ishige, Yuta
    Hamada, Yasumasa
    TETRAHEDRON-ASYMMETRY, 2012, 23 (11-12) : 859 - 866
  • [24] Palladium-Catalyzed Intermolecular Dicarbofunctionalization of Unactivated Alkenes: Synthesis of Fluoroalkylated Heterocycles with All-Carbon Quaternary Centers
    Cheng, Jiajia
    Zhang, Huali
    Lv, Jinliang
    Zheng, Jinhua
    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2022, 2022 (03)
  • [25] Stepwise Construction of All-Carbon Quaternary Centers Starting from Activated Trichloromethyl Group in Three Steps
    He Xinglei
    Ye Keyin
    CHINESE JOURNAL OF ORGANIC CHEMISTRY, 2022, 42 (10) : 3434 - 3435
  • [26] Ruthenium Catalyzed Reductive Coupling of Paraformaldehyde to Trifluoromethyl Allenes: CF3-Bearing All-Carbon Quaternary Centers
    Sam, Brannon
    Montgomery, T. Patrick
    Krische, Michael J.
    ORGANIC LETTERS, 2013, 15 (14) : 3790 - 3793
  • [27] Catalytic Enantioselective Conjugate Alkynylation of β-Aryl-β-trifluoromethyl Enones Constructing Propargylic All-Carbon Quaternary Stereogenic Centers
    Sanz-Marco, Amparo
    Blay, Gonzalo
    Vila, Carlos
    Pedro, Jose R.
    ORGANIC LETTERS, 2016, 18 (15) : 3538 - 3541
  • [28] Construction of All-Carbon Chiral Quaternary Centers through CuI-Catalyzed Enantioselective Reductive Hydroxymethylation of 1,1-Disubstituted Allenes with CO2
    Qiu, Jia
    Gao, Shen
    Li, Chaopeng
    Zhang, Lei
    Wang, Zheng
    Wang, Xiaoming
    Ding, Kuiling
    CHEMISTRY-A EUROPEAN JOURNAL, 2019, 25 (61) : 13874 - 13878
  • [29] First Example of the Intermolecular Palladium-Catalyzed Asymmetric Allylic Alkylation of Hydroxyacrylates: Synthesis of All-Carbon α-Aryl Quaternary Aldehydes
    Asad, Sharif A.
    Ulicki, Joseph
    Shevyrev, Maria
    Uddin, Nazim
    Alberch, Eduardo
    Hossain, M. Mahmun
    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2014, 2014 (26) : 5695 - 5699
  • [30] Catalytic Enantioselective and Diastereoselective Allylic Alkylation with Fluoroenolates: Efficient Access to C3-Fluorinated and All-Carbon Quaternary Oxindoles
    Balaraman, Kaluvu
    Wolf, Christian
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (05) : 1390 - 1395
12345