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

Résultats de recherche: Contribution à un journal/une revue › Article › Revue par des pairs

Résumé

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.

langue originale	Anglais
Pages (de - à)	4046-4050
Nombre de pages	5
journal	Angewandte Chemie. International edition
Volume	58
Numéro de publication	12
Date de mise en ligne précoce	2019
Les DOIs	https://doi.org/10.1002/anie.201814373
Etat de la publication	Publié - 18 mars 2019

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10.1002/anie.201814373

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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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publisher = "John Wiley and Sons Ltd",

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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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U2 - 10.1002/anie.201814373

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

Résumé

Accès au document

Autres fichiers et liens

Empreinte digitale

Équipement

Physico-chimie et caractérisation (PC2)

Spectrométrie de masse (MASUN)

Contient cette citation