1. Rhenium 2-oxoalkyl (enolate) complexes: synthesis and carbon-carbon bond-forming reactions with nitriles
- Author
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Robert G. Bergman, J. J. Doney, Jeffrey G. Stack, and Clayton H. Heathcock
- Subjects
chemistry.chemical_classification ,Nitrile ,Stereochemistry ,Organic Chemistry ,chemistry.chemical_element ,Crystal structure ,Rhenium ,Inorganic Chemistry ,chemistry.chemical_compound ,Crystallography ,Reaction rate constant ,chemistry ,Carbon–carbon bond ,Insertion reaction ,X-ray crystallography ,Physical and Theoretical Chemistry ,Phosphine - Abstract
The (2-oxoalkyl)rhenium complexes (rhenium enolates) (CO){sub 5}ReCH{sub 2}COR{sup 1} (R{sup 1} = OEt, Me, Ph, 1-3) can be prepared on a multigram scale by alkylation of (CO){sub 5}ReNa with ClCH{sub 2}COR{sup 1}. The secondary enolate (CO){sub 5}ReCH(Me)CO{sub 2}Et (4) can also be prepared in a similar fashion with use of MsOCH(Me)CO{sub 2}Et (Ms = CH{sub 3}SO{sub 2}{sup {minus}}). The mono(phosphine) enolates cis-(Ph{sub 3}P)(CO){sub 4}ReCH{sub 2}R{sup 2}(R{sup 2} = CO{sub 2}Et, CO{sub 2}Bu{sup t}, CONEt{sub 2}, COMe, COPh, CN, 8-13) are prepared in high yield via alkylation of (Ph{sub 3}P)(CO){sub 4}ReNa with ClCH{sub 2}R{sup 2}. Synthesis of the secondary enolate cis-(Ph{sub 3}P)(CO){sub 4}ReCH(Me)CO{sub 2}Et (14) is accomplished in 75% yield by alkylation with TfOCH(Me)CO{sub 2}Et (Tf = CF{sub 3}SO{sub 2}{sup {minus}}). The chelating phosphine complex is substitutionally inert under forcing thermal and photochemical conditions. Kinetic studies of the nitrile insertion reaction revealed a weak linear dependence of the rate constant of the reaction on the concentration of added CH{sub 3}CN in benzene; we believe this to be a medium effect.
- Published
- 1990