The Halogen–Samarium Exchange Reaction: Synthetic Applications and Kinetics

Lucile Anthore-Dalion, Andreas D. Benischke, Baosheng Wei, Guillaume Berionni, Paul Knochel

Research output: Contribution to journalArticle

Abstract

Fast I/Sm and Br/Sm exchanges take place when various aromatic or heterocyclic iodides and bromides are treated with nBu2SmCl·4LiCl and nBu3Sm·5LiCl, 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 x 105 faster than the Br/Mg exchange, indicating that the rate of a metalexchange is related to the ionic character of the carbon–metal bond and to the metal electronegativity.
Original languageEnglish
Pages (from-to)4046-4050
Number of pages5
JournalAngewandte Chemie International Edition
Volume58
Issue number12
Early online date2019
DOIs
Publication statusPublished - 18 Mar 2019

Fingerprint

Ketones
Bromides
Acylation
Electronegativity
Kinetics
Imines
Iodides
Aldehydes
Metals

Keywords

  • functionalized organometallics
  • halogensamarium exchange
  • kinetics
  • lanthanides
  • samarium

Cite this

Anthore-Dalion, Lucile ; Benischke, Andreas D. ; Wei, Baosheng ; Berionni, Guillaume ; Knochel, Paul. / The Halogen–Samarium Exchange Reaction : Synthetic Applications and Kinetics. In: Angewandte Chemie International Edition. 2019 ; Vol. 58, No. 12. pp. 4046-4050.
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The Halogen–Samarium Exchange Reaction : Synthetic Applications and Kinetics. / Anthore-Dalion, Lucile; Benischke, Andreas D.; Wei, Baosheng ; Berionni, Guillaume; Knochel, Paul.

In: Angewandte Chemie International Edition, Vol. 58, No. 12, 18.03.2019, p. 4046-4050.

Research output: Contribution to journalArticle

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AU - Benischke, Andreas D.

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AB - Fast I/Sm and Br/Sm exchanges take place when various aromatic or heterocyclic iodides and bromides are treated with nBu2SmCl·4LiCl and nBu3Sm·5LiCl, 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 x 105 faster than the Br/Mg exchange, indicating that the rate of a metalexchange is related to the ionic character of the carbon–metal bond and to the metal electronegativity.

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