Deprotonation of fluoro aromatics using lithium magnesates

被引:40
作者
Awad, H
Mongin, F
Trécourt, F
Quéguiner, G
Marsais, F
Blanco, F
Abarca, B
Ballesteros, R
机构
[1] Univ Rouen, IRCOF, CNRS, Lab Chim Organ Fine & Heterocycl,UMR 6014, F-76131 Mont St Aignan, France
[2] INSA, F-76131 Mont St Aignan, France
[3] Univ Valencia, Fac Farm, Dept Quim Organ, E-46100 Burjassot, Valencia, Spain
关键词
D O I
10.1016/j.tetlet.2004.07.077
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
3-Fluoropyridine was deprotonated on treatment with 1/3equiv of Bu3MgLi in THF at -10degreesC. The lithium arylmagnesate formed was either trapped with electrophiles or involved in a palladium-catalyzed cross-coupling reaction with 2-bromopyridine. The use of a less nucleophilic lithium-magnesium-dialkylamide, (TMP)(3)MgLi, allowed the reaction of 3-fluoroquinoline, giving the 2,2'-dimeric derivative. 2-Fluoropyridine and 2,6-difluoropyridine were deprotonated using 1/3 equiv of the highly coordinated magnesate Bu4MgLi2 in THF at -10degreesC in the presence of a substoichiometric amount of 2,2,6,6-tetramethylpiperidine. 1,3-Difluorobenzene reacted similarly when treated with Bu3MgLi; the reactivity of the base proved to be enhanced by the presence of TMEDA.
引用
收藏
页码:6697 / 6701
页数:5
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