Generation of Aryl and Heteroaryl Magnesium Reagents in Toluene by Br/Mg or Cl/Mg Exchange

The alkylmagnesium alkoxide sBuMgOR⋅LiOR (R=2‐ethylhexyl), which was prepared as a 1.5 m solution in toluene, undergoes very fast Br/Mg exchange with aryl and heteroaryl bromides, producing aryl and heteroaryl magnesium alkoxides (ArMgOR⋅LiOR) in toluene. These Grignard reagents react with a broad r...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-05, Vol.57 (22), p.6701-6704
Main Authors: Ziegler, Dorothée S., Karaghiosoff, Konstantin, Knochel, Paul
Format: Article
Language:English
Subjects:
Aldehydes
Alkoxides
Aromatic compounds
Bromides
Chlorides
Epoxides
Exchanging
Grignard reagents
halogen–magnesium exchange
Ketones
lithium
Magnesium
Reagents
Toluene
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Summary:The alkylmagnesium alkoxide sBuMgOR⋅LiOR (R=2‐ethylhexyl), which was prepared as a 1.5 m solution in toluene, undergoes very fast Br/Mg exchange with aryl and heteroaryl bromides, producing aryl and heteroaryl magnesium alkoxides (ArMgOR⋅LiOR) in toluene. These Grignard reagents react with a broad range of electrophiles, including aldehydes, ketones, allyl bromides, acyl chlorides, epoxides, and aziridines, in good yields. Remarkably, the related reagent sBu2Mg⋅2 LiOR (R=2‐ethylhexyl) undergoes Cl/Mg exchange with various electron‐rich aryl chlorides in toluene, producing diorganomagnesium species of type Ar2Mg⋅2 LiOR, which react well with aldehydes and allyl bromides. Grignard reagents in toluene: The reagent sBuMgOR⋅LiOR (R=2‐ethylhexyl) undergoes very fast Br/Mg exchange, producing aryl and heteroaryl magnesium alkoxides (ArMgOR⋅LiOR) in toluene. Remarkably, these Grignard reagents react with a broad range of electrophiles. The related reagent sBu2Mg⋅2 LiOR (R=2‐ethylhexyl) was used for the first Cl/Mg exchange reactions with aryl chlorides in toluene to give Ar2Mg⋅2 LiOR.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201802123