Vanadium-Catalyzed Solvent-Free Synthesis of Quaternary α-Trifluoromethyl Nitriles by Electrophilic Trifluoromethylation

被引:42
作者
Frueh, Natalja [1 ]
Togni, Antonio [1 ]
机构
[1] ETH, Dept Chem & Angew Biowissensch, CH-8093 Zurich, Switzerland
关键词
nitriles; quaternary centers; solvent-free processes; trifluoromethylation; vanadium; SILYL KETENE IMINES; ASYMMETRIC-SYNTHESIS; OXYTRIFLUOROMETHYLATION; NUCLEOPHILES; REAGENTS;
D O I
10.1002/anie.201406181
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The direct electrophilic trifluoromethylation of silyl ketene imines (SKIs) with hypervalent iodine reagents leads to the formation of quaternary alpha-trifluoromethyl nitriles in good yields. This new reaction has been carried out with a variety of substituted SKIs under solvent-free conditions using a vanadium(IV) catalyst (5 mol%). The corresponding products may be transformed into useful organofluorine building blocks.
引用
收藏
页码:10813 / 10816
页数:4
相关论文
共 41 条
[11]   Nitrile-containing natural products [J].
Fleming, FF .
NATURAL PRODUCT REPORTS, 1999, 16 (05) :597-606
[12]   Nitrile-Containing Pharmaceuticals: Efficacious Roles of the Nitrile Pharmacophore [J].
Fleming, Fraser F. ;
Yao, Lihua ;
Ravikumar, P. C. ;
Funk, Lee ;
Shook, Brian C. .
JOURNAL OF MEDICINAL CHEMISTRY, 2010, 53 (22) :7902-7917
[13]   INTERHALOGEN-CATALYZED CLEAVAGES OF ETHERS AND ESTERS WITH TRIMETHYLSILYL BROMIDE OR CHLORIDE [J].
FRIEDRICH, EC ;
DELUCCA, G .
JOURNAL OF ORGANIC CHEMISTRY, 1983, 48 (10) :1678-1682
[14]   Catalytic Asymmetric Protonation of Silyl Ketene Imines [J].
Guin, Joyram ;
Varseev, Georgy ;
List, Benjamin .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (06) :2100-2103
[15]   Copper-Mediated Cyanotrifluoromethylation of Styrenes Using the Togni Reagent [J].
Ilchenko, Nadia O. ;
Janson, Par G. ;
Szabo, Kalman J. .
JOURNAL OF ORGANIC CHEMISTRY, 2013, 78 (21) :11087-11091
[16]   MOLECULAR-STRUCTURE AND CHEMICAL-REACTIVITY - X-RAY ANALYSES AND C-13-F-19 COUPLING-CONSTANTS OF 1-PHENYL-2,2,2-TRIFLUOROETHYL TOSYLATES [J].
KANAGASABAPATHY, VM ;
SAWYER, JF ;
TIDWELL, TT .
JOURNAL OF ORGANIC CHEMISTRY, 1985, 50 (04) :503-509
[17]  
Kieltsch I, 2008, THESIS ETH ZURICH
[18]  
Kieltsch I., 2007, ANGEW CHEM, V119, P768
[19]   Recent advances in electrophilic CF3-transfer using hypervalent iodine(III) reagents [J].
Kieltsch, Iris ;
Eisenberger, Patrick ;
Stanek, Kyrill ;
Togni, Antonio .
CHIMIA, 2008, 62 (04) :260-263
[20]   Mild electrophilic trifluoromethylation of carbon- and sulfur-centered nucleophiles by a hypervalent iodine(III)-CF3 reagent [J].
Kieltsch, Iris ;
Eisenberger, Patrick ;
Togni, Antonio .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (05) :754-757