The Halogen-Samarium Exchange Reaction: Synthetic Applications and Kinetics

被引：20
|
作者：
Anthore-Dalion, Lucile [1 ]
Benischke, Andreas D. [1 ]
Wei, Baosheng [1 ]
Berionni, Guillaume [2 ]
Knochel, Paul [1 ]
机构：
[1] Ludwig Maximilians Univ Munchen, Dept Chem, Butenandtstr 5-13,Haus F, D-81377 Munich, Germany
[2] Univ Namur, Namur Inst Struct Matter, 61 Rue Bruxelles, B-5000 Namur, Belgium
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2019年 / 58卷 / 12期
关键词：
functionalized organometallics; halogen samarium exchange; kinetics; lanthanides; samarium; MAGNESIUM EXCHANGE; IODINE-MAGNESIUM; ALKENYLMAGNESIUM REAGENTS; ORGANOMAGNESIUM REAGENTS; FUNCTIONALIZED DIARYL; CARBONYL-COMPOUNDS; ORGANIC-SYNTHESIS; GENERATION; BROMINE; HALIDES;
D O I：
10.1002/anie.201814373
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Fast I/Sm and Br/Sm exchanges take place when various aromatic or heterocyclic iodides and bromides are treated with nBu(2)SmCl.4 LiCl and nBu(3)Sm.5 LiCl, respectively. The resulting organosamarium reagents were efficiently quenched with aldehydes, ketones, and imine& Also, they undergo acylations when treated with N,N-dimethylamides leading to ketones. The rate of the Br/Sm exchange for a typical aryl bromide was determined and found to be 8.5 x 10(5) faster than the Br/Mg exchange, indicating that the rate of a metal exchange is related to the ionic character of the carbon-metal bond and to the metal electronegativity.
引用
收藏
页码：4046 / 4050
页数：5
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