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...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie 2019-03, Vol.131 (10), p.3225-3229
Main Authors: Chaumont‐Olive, Pauline, Rouen, Mathieu, Barozzino‐Consiglio, Gabriella, Ben Abdeladhim, Amel, Maddaluno, Jacques, Harrison‐Marchand, Anne
Format: Article
Language:English
Subjects:
(R)-Neobenodin
(R)-Orphenadrin
Aromatic compounds
Chemistry
Chirales Lithiumamidozinkat
Cyanides
Enantiomers
Enantioselektiver Aryltransfer
Esters
Ketones
Lithium
Nitriles
Nukleophile 1,2-Arylierung
Reagents
Substrates
Zincates
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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. Der entscheidende Reaktant in einem enantioselektiven nukleophilen Aryltransfer ist ein dreifach‐koordiniertes Lithiumamidoarylzinkat, dessen chiraler Rest einfach zurückgewonnen und wiederverwendet wird. Die Arylierung toleriert empfindliche funktionelle Gruppen wie Ester, Nitrile, Ketone oder enolisierbare Zentren und setzt Aldehydgruppen in guten Ausbeuten und Enantioselektivitäten um, unabhängig davon, ob der Substituent in ortho‐, meta‐ oder para‐Position ist.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201813510