Enantiopure Ferrocene‐Based Planar‐Chiral Iridacycles: Stereospecific Control of Iridium‐Centred Chirality. Issue 9 (25th January 2016)

• Record Type: Journal Article
• Authors: Arthurs, Ross A.; Ismail, Muhammad; Prior, Christopher C.; Oganesyan, Vasily S.; Horton, Peter N.; Coles, Simon J.; Richards, Christopher J.
• Is Part Of: Chemistry. Volume 22:Issue 9(2016)
• Page Start: 3065
• Page End: 3072
• Publication Date: 2016-01-25
• Subjects: chirality -- enantioselectivity -- ferrocene -- iridacycle -- stereoselectivity; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201504458
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Reaction of [IrCp*Cl2 ]2 with ferrocenylimines (Fc=NAr, Ar=Ph, p ‐MeOC6 H4 ) results in ferrocene C−H activation and the diastereoselective synthesis of half‐sandwich iridacycles of relative configuration S p *, R Ir *. Extension to ( S )‐2‐ferrocenyl‐4‐(1‐methylethyl)oxazoline gave highly diastereoselective control over the new elements of planar chirality and metal‐based pseudo‐tetrahedral chirality, to give both neutral and cationic half‐sandwich iridacycles of absolute configuration S c, S p, R Ir . Substitution reactions proceed with retention of configuration, with the planar chirality controlling the metal‐centred chirality through an iron–iridium interaction in the coordinatively unsaturated cationic intermediate. Abstract : Controlling chirality : The reaction of [IrCp*Cl2 ]2 with ( S )‐2‐ferrocenyl‐4‐(1‐methylethyl)oxazoline results in the diastereoselective synthesis of either cationic or neutral half‐sandwich iridacycles. Excellent control is achieved over the new elements of planar chirality and metal‐based pseudo‐tetrahedral chirality (see figure).