When Chirality Meets "Buchwald-Type" Phosphines: Synthesis and Evaluation in Frustrated Lewis Pair-, Lewis Base- and Palladium-Promoted Asymmetric Catalysis

• Published in: European journal of organic chemistry Vol. 2016; no. 26; pp. 4545 - 4553
• Main Authors: Fer, Mickaël J., Cinqualbre, Joséphine, Bortoluzzi, Julien, Chessé, Matthieu, Leroux, Frédéric R., Panossian, Armen
• Format: Journal Article
• Language: English
• Published: WEINHEIM Blackwell Publishing Ltd 01.09.2016; Wiley; Wiley Subscription Services, Inc; Wiley-VCH Verlag
• Subjects: Asymmetric catalysis; Atropoisomerism; Axial chirality; Biaryls; Catalysis; Chemical Sciences; Chemistry; Chemistry, Organic; Enantioselectivity; Homogeneous catalysis; Organic chemistry; Organocatalysis; Palladium; Phosphines; Physical Sciences; Science & Technology; Enantioselectivity; Axial chirality; HYDROSILYLATION; Palladium; MONOPHOSPHINE LIGANDS; ALLENES; Organocatalysis; Asymmetric catalysis; BETA-BORATION; AMINATION; Atropoisomerism; ORGANOCATALYSTS; Homogeneous catalysis; ATROPOSELECTIVE SYNTHESIS; OLEFINS; Biaryls; BAYLIS-HILLMAN; Phosphines
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201600727

We describe the synthesis of axially chiral “Buchwald ligand”‐like biphenylphosphines in highly enantioenriched form. These monodentate phosphines, biphenyl analogues of Hayashi's MOP ligands, were evaluated in phosphine‐promoted organocatalysis and in hydrosilylations catalyzed by palladium or by frustrated Lewis pairs. As expected, the title phosphines appeared best suited for transition metal catalysis where they provided higher asymmetric induction. Axially chiral “Buchwald ligand”‐like biphenylphosphines were prepared in highly enantioenriched form and were evaluated in phosphine‐promoted organocatalysis and hydrosilylations catalyzed by Pd or by frustrated Lewis pairs (FLPs). The title phosphines are best suited for transition metal catalysis where asymmetric induction proved much higher.