The solution structures of chiral Ti4+ alkoxides. II. The roles of diolate basicity and side-chain binding group polarity

Abstract

With a view to reproduce the structure in solution of the Katsuki–Sharpless catalyst (the dimeric complex formed by homochiral diisopropyl tartrate with Ti(OiPr)4), five C2-symmetric chiral 2,3-butanediols, related to L-threitol but bearing N-, S-, and P-containing groups at the 1- and 4-positions, were prepared and their reactions with Ti(OiPr)4 were examined by nuclear magnetic resonance spectroscopy. The 1,4-dithioether formed a non-fluxional 2:2 tricyclic complex entirely analogous to those formed by alkylated sugar derivatives. The related disulfone formed a similar complex, but only at low temperatures, probably because of oligomerization at higher temperatures. A symmetric 2:1 complex also formed with excess Ti(OiPr)4, but incompletely and in equilibrium with the 2:2 species. No well-defined complexes were formed with pyrazole or phosphine oxide functionalities. However, in the presence of trifluoroacetic acid (TFA), a 1:2:2 L:Ti:TFA complex was identified with the dimethylpyrazole-containing diol and this resembled the 2:3 complexes formed by tartramides. Generally, the degree of spectral asymmetry and the coupling constant between diolate protons were instrumental in assigning structures and were used to classify all chiral diolate complexes into two groups according to whether or not they exhibited metal chelation and diolate bridging. By comparison of the effects of complexation on the diolate nuclei, a correlation was found between 13C and 1H nmr signal positions and between the pairs of signals in the spectra of asymmetric complexes, except in four cases where metal-bound side-chain groups induced a shielding of the bridging diolate proton. This could serve as an additional indication of metal chelation and diolate bridging and confirmed that nuclei at bridging positions appeared upfield of terminal ones. Noting that all the diols that readily chelated and bridged possessed electron-releasing side chains, while tartrates and tartramides that did not chelate possessed electron-withdrawing side chains, the basicity of the diolate oxygens is considered the most important determinant of structure. Side-chain polarity was instead found to influence whether or not a well-defined complex could form.