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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

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journal contribution
posted on 26.08.1998, 00:00 by James M. Longmire, Xumu Zhang, Maoyu Shang
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)23-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.