Designing chiral rhenium (VII) trioxo complexes Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/rb68xh458

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  • The epoxide deoxygenation reaction is formally the reverse of theepoxidation reaction. Compared to epoxidation
  • The epoxide deoxygenation reaction is formally the reverse of theepoxidation reaction. Compared to epoxidation, which has reached its fullmaturity, epoxide deoxygenation has not been as intensively developed.Among the few deoxygenation reagents, a handful are catalytic in a metalcomplex, show high stereospecificity and operate under mild conditions. Acommon feature of all present deoxygenation reagents is that they do notperform asymmetric deoxygenation of racemic epoxides.Rhenium (VII) trioxo complexes are emerging as pliable catalysts forepoxide deoxygenation. Designing a chiral rhenium (VII) trioxo complexwas our goal. Guided by the mechanism of rhenium (VII) trioxo catalyzedepoxide deoxygenation and the mechanism of the stereogenic informationtransfer, we have designed and prepared a chiral rhenium(VII) trioxocomplex. This complex is void of stereogenic centers and the source ofasymmetry is the restricted rotation around a carbon-carbon bond.Detailed conformational analysis of the new chiral complex was done byextensive NMR measurements and molecular modeling. The rotationbarrier for the diolate was experimentally and computationally estimated tobe 9.72 kcal by mol and 8.06 kcal by mol, respectively.Unsuccessful attempts were made to prepare a camphor basedscorpionate because of the extreme steric congestion. A menthone basedscorpionate was successfully prepared. The related rhenium (TII) trioxocomplex with this scorpionate revealed contradicting chemical andspectroscopic features.
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