Resorcinarene‐Based o‐Biarylphosphines in Palladium‐Catalysed Suzuki–Miyaura Cross‐Coupling Reactions of Bulky Substrates. Issue 3 (23rd January 2017)

• Record Type: Journal Article
• Authors: Elaieb, Fethi; Sémeril, David; Matt, Dominique
• Is Part Of: European journal of inorganic chemistry. Issue 3(2017)
• Page Start: 685
• Page End: 693
• Publication Date: 2017-01-23
• Subjects: Resorcinarene -- Cavitands -- Phosphines -- Palladium -- Cross‐coupling; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201601270
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Two o ‐biarylphosphines, in which the arene ring remote from the phosphorus atom is part of a resorcin[4]arene cavitand, have been synthesised, characterised by X‐ray diffraction and assessed in the cross‐coupling reactions of bulky aryl chlorides with sterically hindered arylboronic acids. Only atropisomers with externally located P atoms were obtained. The resorcinarene ligand with the o ‐PCy2 C6 H4 substituent was found to be more efficient than the Buchwald analogue SPhos in catalysing coupling reactions, reacting around 1.4 times faster. Its superior performance has been attributed to the permanent exo positioning of the metal centre, which engenders steric interactions with two pentyl substituents and therefore facilitates the reductive elimination step. Abstract : The introduction of a 2‐(dicyclohexylphosphino)phenyl unit as a substituent directly attached to a resorcinarene cavitand has been found to be a useful Buchwald‐type ligand for the palladium‐catalysed Suzuki–Miyaura cross‐coupling of bulky aryl chlorides with sterically hindered arylboronic acids. This phosphine was found to be a superior ligand to SPhos, an analogue devoid of a cavity.