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  The Preparation and Resolution of Novel Axially Chiral Pyrazine-Containing P,N Ligands for Asymmetric Catalysis and Their Application in Palladium-Catalysed Allylic Substitution

Kelly, S., Goddard, R., & Guiry, P. J. (2022). The Preparation and Resolution of Novel Axially Chiral Pyrazine-Containing P,N Ligands for Asymmetric Catalysis and Their Application in Palladium-Catalysed Allylic Substitution. Helvetica Chimica Acta, 105(1): e202100205. doi:10.1002/hlca.202100205.

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 Creators:
Kelly, Sarah1, Author
Goddard, Richard2, Author              
Guiry, Patrick J.1, Author
Affiliations:
1School of Chemistry, Centre for Synthesis and Chemical Biology, University College Dublin, Belfield, IE-Dublin 4, Ireland, ou_persistent22              
2Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445625              

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Free keywords: allylic alkylation; mechanistic studies; N,P ligands; palladium
 Abstract: The design and synthesis of two novel pyrazine-containing ligands, 3,6-diisopropyl-Pyrazinap and Np−Cy-Pyrazinap, has been described. Their synthesis was accomplished in six and nine steps, respectively, in which the key steps were the formation of the biaryl linkage through a Suzuki cross-coupling reaction and the formation of the aryl to phosphorus bond employing nickel catalysis. Both ligands were resolved through the formation of diastereomeric palladacycles and in the case of the isolated diastereomer formed from 3,6-diisopropyl-Pyrazinap, an X-ray crystal structure showed the axial chirality to possess (S)-configuration. The two enantiopure ligands were applied to the palladium-catalysed allylic alkylation of 1,3-diphenylprop-2-enyl acetate with dimethyl malonate and afforded conversions of up to 100 % and 99 % with enantioselectivities of up to 92 % ee and 78 % ee, respectively. A series of 1,1,3-triphenylallyl and 1,3-diphenylallyl palladium complexes were prepared and their solution structures and dynamic behaviour elucidated by 2D-COSY and NOESY NMR spectroscopic experiments.

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Language(s): eng - English
 Dates: 2021-10-012021-11-242022-01-19
 Publication Status: Published online
 Pages: 26
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/hlca.202100205
 Degree: -

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Title: Helvetica Chimica Acta
  Abbreviation : Helv. Chim. Acta
Source Genre: Journal
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Publ. Info: Zürich : Verlag Helvetica Chimica Acta AG
Pages: - Volume / Issue: 105 (1) Sequence Number: e202100205 Start / End Page: - Identifier: ISSN: 0018-019X
CoNE: https://pure.mpg.de/cone/journals/resource/954925403620