ABSTRACT
One-pot syntheses of three new enantiopure heteroscorpionate ligands derived from (+)-camphor or (-)-menthone are described. The ligands are obtained by reacting pyrazoles derived from (+)-camphor or (-)-menthone with sodium hydride and thionyl chloride. Subsequent reactions with pyridine and various aldehydes afford the tripod ligands in multi-gram amounts. Especially the menthopyrazole based ligand 6 showed encouraging ee values up to 69% in the Cu(I) catalysed enantioselective cyclopropanation of styrene with ethyl diazoacetate.
Subject(s)
Camphor/chemistry , Copper/chemistry , Menthol/chemistry , Aldehydes/chemistry , Catalysis , Coordination Complexes/chemical synthesis , Coordination Complexes/chemistry , Crystallography, X-Ray , Ligands , Molecular Conformation , Pyridines/chemistry , Sodium Compounds/chemistry , Stereoisomerism , Sulfur Oxides/chemistryABSTRACT
Reductive S-S bond cleavage of a disulfide precursor obtained from a pyridine-catalyzed Peterson-type reaction starting from camphorpyrazole , thionyl chloride and 2-methyl-2-(methyldithio)propionaldehyde yields 2,2'-bis(camphorpyrazol-1-yl)-2-methylpropane-2-thiol (HSiprbpm3cam, ); the first zinc complexes bearing this ligand exhibit kappa3 coordination of the ligand.
