TetraPh-Tol-BITIOPO: a new atropisomeric 3,3′-bithiophene based phosphine oxide as an organocatalyst in Lewis base-catalyzed Lewis acid mediated reactions

A new chiral phosphine oxide based on a 3,3′-bithiophene scaffold (TetraPh-Tol-BITIOPO) was synthesized, fully characterized and separated into antipodes through chiral HPLC. This new compound was successfully employed as an organocatalyst in Lewis base-catalyzed Lewis acid mediated reactions involv...

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Bibliographic Details
Published in:Organic & biomolecular chemistry 2019-08, Vol.17 (32), p.7474-7481
Main Authors: Mirco, Abbinante Vincenzo, Maurizio, Benaglia, Sergio, Rossi, Tiziana, Benincori, Roberto, Cirilli, Marco, Pierini
Format: Article
Language:English
Subjects:
Absolute configuration
Aldehydes
Allyl compounds
Antipodes
Catalysis
Catalysts
Chemical reactions
Computer applications
High-performance liquid chromatography
Ketones
Lewis acid
Lewis base
Liquid chromatography
Organic chemistry
Phosphine
Phosphine oxide
Thioesters
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Summary:A new chiral phosphine oxide based on a 3,3′-bithiophene scaffold (TetraPh-Tol-BITIOPO) was synthesized, fully characterized and separated into antipodes through chiral HPLC. This new compound was successfully employed as an organocatalyst in Lewis base-catalyzed Lewis acid mediated reactions involving trichlorosilyl compounds. The new atropisomeric catalyst was able to promote the allylation of aldehydes with allyltrichlorosilane in up to 98% yield and up to 96% enantiomeric excess (ee), and the direct aldol reaction to afford β-hydroxy ketones and β-hydroxy thioesters, with good chemical yields and modest stereochemical efficiency. Computational studies helped to elucidate and to rationalize the stereochemical outcome of the reactions catalyzed by TetraPh-Tol-BITIOPO that was found to favour the formation of the isomer with an opposite absolute configuration in comparison with the products obtained with the previously reported 3,3′-bithiophene-based catalyst. A new chiral phosphine oxide based on a 3,3′-bithiophene scaffold (TetraPh-Tol-BITIOPO) was synthesized, fully characterized and separated into antipodes through chiral HPLC.
ISSN:1477-0520
1477-0539
DOI:10.1039/c9ob01297d