Didentate ligands synthesis

The N,P phosphine-oxazoline chelate (59) is chiral, and complexes can act as homogeneous catalysts for asymmetric synthesis the Ir(l) and Pd(II) complexes promote enantioselective olefin hydrogenation and allylic substitution respectively. An N,P analog of the N,N didentate ligand 2,2 -bipyridine is (60), the soft P donor helping to stabilize low-valent metals. Further, 2,2-bipyridine derivatives such as (61) can bind metals such as Ir and Ru as N,C chelates with one pyridine nitrogen rotated to the opposite side, away from the metal ion. 

The present paper describes the synthesis of N-(2-hydroxyethyl)-3,5-dimethylpyrazole and the synthesis of the tosylated compound N-(2-p-tol-uenesulfonylethyl)-3,5-dimethylpyrazole which can be used for the synthesis of larger chelating ligands. The tosylation is carried out in a water/acetone mixture, unlike most classical tosylations, which are performed in pyridine.7 A high yield of pure tosylated product is obtained from this reaction. A water/acetone mixture as the solvent for the synthesis of other tosylates may very well be also successful. Since the compound N-(2-hydroxyethyl)-3,5-dimethylpyrazole may itself act as a didentate N,0 ligand in coordination compounds with transition metal ions,9 an example using Cu(II) is provided below. 

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