The Halogen–Samarium Exchange Reaction: Synthetic Applications and Kinetics

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

doi:10.1002/anie.201814373

The Halogen–Samarium Exchange Reaction: Synthetic Applications and Kinetics

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

Namur Institute of Structured Matter

Research output: Contribution to journal › Article › peer-review

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 language	English
Pages (from-to)	4046-4050
Number of pages	5
Journal	Angewandte Chemie. International edition
Volume	58
Issue number	12
Early online date	2019
DOIs	https://doi.org/10.1002/anie.201814373
Publication status	Published - 18 Mar 2019

Keywords

functionalized organometallics
halogensamarium exchange
kinetics
lanthanides
samarium
halogen–samarium exchange

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10.1002/anie.201814373

Cite this

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title = "The Halogen–Samarium Exchange Reaction: Synthetic Applications and Kinetics",

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.",

keywords = "functionalized organometallics, halogensamarium exchange, kinetics, lanthanides, samarium, halogen–samarium exchange",

author = "Lucile Anthore-Dalion and Benischke, {Andreas D.} and Baosheng Wei and Guillaume Berionni and Paul Knochel",

note = "Funding Information: We thank the LMU Munich for financial support and the Humboldt foundation for a fellowship to L. A.-D. We also thank Albemarle (Frankfurt) and BASF (Ludwigshafen) for the generous gift of chemicals. Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Copyright: Copyright 2019 Elsevier B.V., All rights reserved.",

year = "2019",

month = mar,

day = "18",

doi = "10.1002/anie.201814373",

language = "English",

volume = "58",

pages = "4046--4050",

journal = "Angewandte Chemie. International edition",

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T2 - Synthetic Applications and Kinetics

AU - Anthore-Dalion, Lucile

AU - Benischke, Andreas D.

AU - Wei, Baosheng

AU - Berionni, Guillaume

AU - Knochel, Paul

N1 - Funding Information: We thank the LMU Munich for financial support and the Humboldt foundation for a fellowship to L. A.-D. We also thank Albemarle (Frankfurt) and BASF (Ludwigshafen) for the generous gift of chemicals. Publisher Copyright: © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Copyright: Copyright 2019 Elsevier B.V., All rights reserved.

PY - 2019/3/18

Y1 - 2019/3/18

N2 - 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.

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.

KW - functionalized organometallics

KW - halogensamarium exchange

KW - kinetics

KW - lanthanides

KW - samarium

KW - halogen–samarium exchange

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DO - 10.1002/anie.201814373

M3 - Article

SN - 1433-7851

VL - 58

SP - 4046

EP - 4050

JO - Angewandte Chemie. International edition

JF - Angewandte Chemie. International edition

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ER -

The Halogen–Samarium Exchange Reaction: Synthetic Applications and Kinetics

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Physical Chemistry and characterization(PC2)

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The Halogen–Samarium Exchange Reaction: Synthetic Applications and Kinetics

Abstract

Keywords

Access to Document

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Mass Spectrometry Service

Physical Chemistry and characterization(PC2)

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