Chiral Pt(II)/Pd(II) pincer complexes that show C-H center dot center dot center dot Cl hydrogen bonding: Synthesis and applications to catalytic asymmetric aldol and silylcyanation reactions

Abstract

A chiral C-2-symmetric NCN ligand, (5R,7R)-1,3-bis(6,6-dimethyl-5,6,7,8-tetrahydro-5,7-methanoquinolin-2-yl)benzene has been synthesized. A direct cyclometalation of this ligand with K2MCl4 (M = Pt, Pd) in dry acetic acid offered the corresponding pincer complexes, [(5R,7R)-1,3-bis(6,6-dimethyl-5,6,7,8-tetrahydro-5,7-methanoquinolin-2-yl)phenyl]platinum(II) chloride 5a and its palladium(II) analogue 5b. The Pt(II) and Pd(II) complexes 5 were characterized by NMR spectroscopy, and X-ray crystal structure analysis was done for the Pt(II) complex. The NMR data for both the complexes and X-ray crystal structural data for the chloro-Pt(II) complex indicate the existence of intramolecular C-H center dot center dot center dot Cl hydrogen bonding both in solution and in solid states. Chloride abstraction from 5a by treatment with silver triflate resulted in the corresponding triflate complex 6a, which generates the corresponding cationic aqua complex 7a in the presence of water molecules. The Pt(II) complex 6a/7a was used as asymmetric catalyst in the aldol reaction between methyl isocyanoacetate and aldehydes and also in the silylcyanation of aldehydes. (c) 2006 Elsevier B.V. All rights reserved.