124378-94-5Relevant articles and documents
Rhenium 2-oxoalkyl (enolate) complexes. Synthesis and carbon-carbon bond-forming reactions with nitriles
Stack,Doney,Bergman,Heathcock
, p. 453 - 466 (2008/10/08)
Several carbon-bound rhenium enolates, based on (C-O)5Re and (Ph3P)(CO)4Re, can be prepared by alkylation of the corresponding carbonylmetalate anions with α-chloro carbonyl or α-sulfonyloxy carbonyl compounds. These materials can be isolated by standard chromatographic methods and are air-stable in solution and the solid state. Irradiation of the (CO)5Re derivatives led to decomposition. Thermal activation of these compounds required elevated temperatures, which in the presence of Ph3P and a nitrile resulted in the formation of carbon-carbon bond between the enolate and nitrile carbon atoms. The mechanism of the nitrile/enolate condensation has been examined and is proposed to proceed through a Ph3P-substituted nitrile complex. This complex was synthesized independently, and its efficacy as an intermediate was demonstrated. Labile derivatives of the Ph3P-substituted enolates were prepared by reaction of the enolates with Me3NO in CH3CN. Acetonitrile complexes are obtained for the ester and nitrile enolates.
