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38653-B1
Kinetic Resolution of Secondary Alkyl Halides via Enantioselective Dehalogenation with Chiral Transition Metal Complexes
Kyle S. Knight, University of Tennessee (Chattanooga)
We have successfully developed a system for the dehalogenation of secondary alkyl halides using palladium catalysts and chelating diphosphine ligands. Alkyl halides have been dehalogenated in the presence palladium complexes, ethyl Grignard reagents, and diisobutylaluminum hydride. We have found that the reaction was successful in the dehalogenation of a variety of secondary alkyl halides, a class of compounds that are considered unreactive to oxidative addition by palladium(0) complexes.
These studies provide evidence of unprecedented reactivity of organopalladium intermediates with secondary alkyl halides. Mechanistic experiments suggest that the reduction involves an oxidative addition mechanism, and is not a radical or metal exchange process. Our attempts at kinetic resolution using chiral catalysts derived from (BINAP)PdCl2 have not shown significant enantioselectivity. Other chiral bidentate phosphorus ligands were also examined without significant improvement.
Additionally, we have collaborated with Andrew Gellman, in his work studying the enantioselective surface chemistry of R-2-bromobutane on the chiral surfaces Cu(643) R&S and Cu (531) R&S.
In a second area of research, we have performed a structure-reactivity study on the pyridinium chlorochromate promoted oxidative cyclization of bishomoallylic tertiary alcohols to yield substituted tetrahydrofurans.
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