title: On the nature of the oxidative heterocoupling of lithium enolates.
abstract: The coupling of enolates through single-electron oxidation is one of the most direct routes for generating 1,4-dicarbonyls. Recent work on the intermolecular heterocoupling of equimolar amounts of two different enolates through single-electron oxidation has shown that synthetically useful yields beyond those predicted by statistics can be obtained. To determine the underlying basis for the selective formation of heterocoupled products, kinetic, (7)Li NMR, and synthetic studies were performed. The collection of data obtained from these experiments shows that the selective formation of heterocoupled products is a consequence of heteroaggregation of lithium enolates.
authors: Department of Chemistry, Lehigh University, Bethlehem, Pennsylvania 18015, USA.
authors: Brian M
authors: BM
authors: Casey
authors: Robert A
authors: RA
authors: Flowers
mesh_terms: D007659:Ketones / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D013237:Stereoisomerism
chemical_list: D007659:Ketones; D009942:Organometallic Compounds; D008094:Lithium