Synthesis and X-ray Crystal Structures of Palladium(II) and Platinum(II) Complexes of the PCP-Type Chiral Tridentate Ligand (1R,1‘R)-1,3-Bis[1-(diphenylphosphino)ethyl]benzene. Use in the Asymmetric Aldol Reaction of Methyl Isocyanoacetate and Aldehydes

Citations Over TimeTop 10% of 1998 papers

Abstract

Enantiomerically pure (1R,1‘R)-1,3-bis[1-(diphenylphosphino)ethyl]benzene (4) has been obtained for the first time. The key step involves in situ tosylation of chiral (1S,1‘S)-dimethyl-1,3-benzenedimethanol (6) followed by nucleophilic attack with LiPPh2(BH3) to give [(1R,1‘R)-1,3-bis[1-(diphenylphosphino)ethyl]benzene]−bisborane (7). The bisborane-protected phosphine can be easily handled and purified before deprotecting with HBF4·OMe2 to give the title compound. [(1R,1‘R)-2,6-bis[1-(diphenylphosphino)ethyl]phenyl]chloropalladium(II) (9) and the platinum(II) analogue (8) were synthesized through reaction of the chiral PCP-type ligand with PdCl2(PhCN)2 and [Pt2(μ-Cl)2(η3-CH2C(CH3)CH2)2], respectively, and their X-ray crystal structures were determined. Removal of chloride with AgOTf provided an active catalyst species for the asymmetric aldol reaction of methyl isocyanoacetate and aldehydes.

Related Papers

• → Metal-catalyzed asymmetric aldol reactions(2012)24 cited
• → First Catalytic Aldol-Transfer Reaction via Aluminum Enolates: A New Way To Generate Aldol Adducts of Aldehydes from Aldol Adducts of Ketones(2000)30 cited
• → Direct Catalytic Asymmetric Aldol Reaction Using Chiral Metal Complexes(2004)32 cited
• → Studies in Organocatalysts Synthesis for Direct Aldol Reaction(2013)
• High Enantioselective Organocatalytic Asymmetric Direct Aldol Reactions of Aldehydes with Long-Chain Aliphatic Ketones(2009)