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The Halogen–Samarium Exchange Reaction: Synthetic Applications and Kinetics
Author(s) -
AnthoreDalion Lucile,
Benischke Andreas D.,
Wei Baosheng,
Berionni Guillaume,
Knochel Paul
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201814373
Subject(s) - chemistry , halogen , reagent , electronegativity , metal , samarium , aryl , bromide , medicinal chemistry , ionic bonding , inorganic chemistry , organic chemistry , ion , alkyl
Fast I/Sm and Br/Sm exchanges take place when various aromatic or heterocyclic iodides and bromides are treated with n Bu 2 SmCl⋅4 LiCl and n Bu 3 Sm⋅5 LiCl, respectively. The resulting organosamarium reagents were efficiently quenched with aldehydes, ketones, and imines. 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 8.5×10 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.