Mechanism of Orbital Interactions in the Sharpless Epoxidation with Ti(IV) Peroxides: A DFT Study.

The M06-2X DFT functional has been employed to examine monomeric titanium(IV) hydroperoxo catalysts that model the individual steps in the dimeric titanium(IV)-catalyzed Sharpless reaction. This is the first example of a transition structure for titanium(IV) -butyl hydroperoxide-catalyzed epoxidation that describes the molecular motion required for oxygen atom transfer. These epoxidation catalysts have been examined for both bimolecular reactions with E-2-butene and the intramolecular epoxidation of allyl alcohol. The transition structure for the bimolecular peroxyacetic acid epoxidation of E-2-butene has been shown to be spiro in nature, and likewise, the intramolecular epoxidation of allyl alcohol is also nearly spiro. The significance of the O-C-C═C dihedral angle of allyl alcohol is examined for the Ti(IV) -butyl hydroperoxide epoxidation mechanism. Evidence is presented that supports a hexacoordinate titanium peroxo environment that exists in the dimeric form of the Sharpless catalyst. The mechanism for a 1,3-rearrangement of the alkoxide ligand in a titanium hydroperoxide to the Ti center in concert with oxygen atom transfer of the proximal oxygen to the C═C bond of the substrate is presented. The dimerization of Ti(IV)-(R,R)-diethyl tartrate-diisopropoxide and its hydrolysis have been calculated. The mechanism for rapid ligand exchange with alkyl hydroperoxides involving the Ti(O--Pr) precursor is examined to show how the active epoxidation catalyst is produced.