Photoredox-Coupled F-Nucleophilic Addition: Allylation of gem-Difluoroalkenes

被引:102
作者
Liu, Haidong [1 ]
Ge, Liang [1 ]
Wang, Ding-Xing [1 ]
Chen, Nan [1 ]
Feng, Chao [1 ]
机构
[1] Nanjing Tech Univ, Sch Chem & Mol Engn, Inst Adv Synth, Nanjing 210009, Jiangsu, Peoples R China
基金
中国国家自然科学基金;
关键词
allylic compounds; fluorine; photochemistry; radicals; reaction mechanisms; C-H AMINATION; CROSS-COUPLINGS; TRIFLUOROMETHYLATION; LIGHT; BOND; ACTIVATION; GENERATION; CATALYSIS; FLUORINE; RADICALS;
D O I
10.1002/anie.201814308
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A novel strategy for the expedient construction of CF3-embeded tertiary/quartentary carbon centers was developed by taking advantage of photoredox catalysis. Thanks to a key step of single-electron oxidation, electron-rich gem-difluoroalkenes, which otherwise are essentially reluctant towards F-nucleoplilic addition, now readily participate in this fluoroallylation reaction. Furthermore, this strategy provides an elegant example for the generation, as well as functionalization, of alpha-CF3 -substituted benzylic radical intermediates using cheap and readily available starting materials.
引用
收藏
页码:3918 / 3922
页数:5
相关论文
共 89 条
[31]   Benzylic C(sp3)-H Perfluoroalkylation of Six-Membered Heteroaromatic Compounds [J].
Kuninobu, Yoichiro ;
Nagase, Masahiro ;
Kanai, Motomu .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (35) :10263-10266
[32]  
Lang S. B, 2017, ANGEW CHEM, V129, P15269
[33]   Photoredox Generation of Carbon-Centered Radicals Enables the Construction of 1,1-Difluoroalkene Carbonyl Mimics [J].
Lang, Simon B. ;
Wiles, Rebecca J. ;
Kelly, Christopher B. ;
Molander, Gary A. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (47) :15073-15077
[34]  
Li Q., 2016, ANGEW CHEM, V128, P13506
[35]  
Liang Y., 2015, ANGEW CHEM, V127, P9175
[36]   Stereoconvergent Negishi Arylations of Racemic Secondary Alkyl Electrophiles: Differentiating between a CF3 and an Alkyl Group [J].
Liang, Yufan ;
Fu, Gregory C. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (30) :9523-9526
[37]   Nickel-Catalyzed Alkyl-Alkyl Cross-Couplings of Fluorinated Secondary Electrophiles: A General Approach to the Synthesis of Compounds having a Perfluoroalkyl Substituent [J].
Liang, Yufan ;
Fu, Gregory C. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (31) :9047-9051
[38]   One-Pot Photomediated Giese Reaction/Friedel-Crafts Hydroxyalkylation/Oxidative Aromatization To Access Naphthalene Derivatives from Toluenes and Enones [J].
Liu, Haiwang ;
Ma, Lishuang ;
Zhou, Rong ;
Chen, Xuebo ;
Fang, Weihai ;
Wu, Jie .
ACS CATALYSIS, 2018, 8 (07) :6224-6229
[39]   Trifluoromethyltrimethylsilane: Nucleophilic Trifluoromethylation and Beyond [J].
Liu, Xiao ;
Xu, Cong ;
Wang, Mang ;
Liu, Qun .
CHEMICAL REVIEWS, 2015, 115 (02) :683-730
[40]   Direct C-H Cyanation of Arenes via Organic Photoredox Catalysis [J].
McManus, Joshua B. ;
Nicewicz, David A. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (08) :2880-2883