Synthesis of Atropisomeric MeOBIPHEP Analogues and Their Application in Silver-Catalyzed Cycloisomerization of Allenols

The preparation of novel MeOBIPHEP atropisomeric chiral congener ligands via an efficient palladium-catalyzed P-C coupling key step is described. We demonstrate that these palladium-catalyzed conditions are compatible with the brominated MeOBIPHEP backbone. The reaction conditions for asymmetric sil...

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Bibliographic Details
Published inSynthesis (Stuttgart) Vol. 48; no. 19; pp. 3309 - 3316
Main Authors d'Herouville, Florent Le Boucher, Millet, Anthony, Scalone, Michelangelo, Michelet, Veronique
Format Journal Article
LanguageEnglish
Published STUTTGART Thieme Medical Publishers 04.10.2016
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
TANDEM REACTIONS
CASCADE REACTIONS
UNPROTECTED 2-ALKYNYLANILINES
DOMINO HYDROARYLATION/CYCLOISOMERIZATION REACTIONS
asymmetric catalysis
GOLD COMPLEXES
allenols
atropisomeric ligands
NATURAL-PRODUCT SYNTHESIS
LIGANDS
HETEROCYCLES
silver
cycloisomerization
COINAGE METALS
DYNAMIC SOLUTION BEHAVIOR
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Summary:The preparation of novel MeOBIPHEP atropisomeric chiral congener ligands via an efficient palladium-catalyzed P-C coupling key step is described. We demonstrate that these palladium-catalyzed conditions are compatible with the brominated MeOBIPHEP backbone. The reaction conditions for asymmetric silver-catalyzed cycloisomerization of gamma-allenols were optimized, leading to the first enantioselective catalytic system employing atropisomeric diphosphine ligands as the chiral inducer. The process follows a major 5-exo cyclization via addition of the alcohol moiety to the p-activated allenyl intermediate, leading to vinyltetrahydrofurans with enantiomeric ratios up to 91.5:8.5.
ISSN:0039-7881
1437-210X
DOI:10.1055/s-0035-1562448