Chiral Lithium Amido Aryl Zincates: Simple and Efficient Chemo‐ and Enantio‐Selective Aryl Transfer Reagents

An enantioselective aryl transfer is promoted using chiral tricoordinated lithium amido aryl zincates that are easily accessible reagents and whose chiral appendage is simply recovered for reuse. The arylation reaction is run in good yields (60 % average on twenty substrates) and high enantiomeric e...

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Veröffentlicht in:Angewandte Chemie International Edition 2019-03, Vol.58 (10), p.3193-3197
Hauptverfasser: Chaumont‐Olive, Pauline, Rouen, Mathieu, Barozzino‐Consiglio, Gabriella, Ben Abdeladhim, Amel, Maddaluno, Jacques, Harrison‐Marchand, Anne
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container_issue 10
container_start_page 3193
container_title Angewandte Chemie International Edition
container_volume 58
creator Chaumont‐Olive, Pauline
Rouen, Mathieu
Barozzino‐Consiglio, Gabriella
Ben Abdeladhim, Amel
Maddaluno, Jacques
Harrison‐Marchand, Anne
description An enantioselective aryl transfer is promoted using chiral tricoordinated lithium amido aryl zincates that are easily accessible reagents and whose chiral appendage is simply recovered for reuse. The arylation reaction is run in good yields (60 % average on twenty substrates) and high enantiomeric excesses (95 % ee average). This occurs whatever the ortho, meta, or para substituent borne by the substrate and a complete chemoselectivity is observed with respect to the aldehyde function. Sensitive groups such as nitriles, esters, ketones, and enolisable substrates resist to the action of the ate reagent, warranting a large scope to this methodology. Chemo‐ and enantio‐selective nucleophilic aryl transfer: The key reactant is a chiral tricoordinated lithium amido aryl zincate of which the chiral appendage is simply recovered and reused. The arylation leaves intact sensitive functions such as esters, nitriles, ketones or enolisable sites, while running with aldehyde groups in good yields and high ee values, this whatever the ortho, meta, or para substituent borne by the substrate if aromatic.
doi_str_mv 10.1002/anie.201813510
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source Wiley Online Library Journals Frontfile Complete
subjects (R)-Neobenodine
(R)-Orphenadrine
Aromatic compounds
Chemical Sciences
chiral lithium amido zincate
Cyanide
Enantiomers
enantioselective aryl transfer
Esters
Ketones
Lithium
Nitriles
nucleophilic 1,2 arylation
Organic chemistry
Reagents
Substrates
Zincates
title Chiral Lithium Amido Aryl Zincates: Simple and Efficient Chemo‐ and Enantio‐Selective Aryl Transfer Reagents
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