novel doubly borylated enolate is identified as an intermediate of the double aldol reaction of acetate esters. As a precursor to the formation of the doubly borylated enolate, carbon-bound boron enolates of carboxylic esters are spectroscopically characterized for the first time. When 2,6-diisopropylphenyl acetate (10d) is treated with c-Hex(2)BOTf (1.3 equiv) and triethylamine (1.5 equiv) in CDCl3, the corresponding mono-enolate is formed as a mixture of oxygen- (11d) and carbon-bound (12d) forms in 71% and 20% yields, respectively. The structures of these enolates have been unambiguously determined by NMR spectroscopy. Investigation of the enolization of a series of substituted aryl acetates shows that the steric factor of the acetate affects the degree of the mono-enolate (as a mixture of oxygen- and carbon-bound enolates) and the doubly borylated enolate formation. Studies also revealed that oxygen- and carbon-bound boron enolates exist as equilibrium mixtures and that a proton transfer process occurs between oxygen- and carbon-bound enolates. The doubly borylated enolate formation is general for a variety of carbonyl compounds. Besides acetate esters, carbonyl containing compounds, such as acetic acid, dimethylacetamide, methoxyacetone, and 3-acetyl-2-oxazolidinone, also produce the doubly borylated enolates when treated with c-Hex(2)BOTf (2.5 equiv) and triethylamine (3.0 equiv). A plausible pathway of the double aldol reaction involving a carbon-bound boron enolate as a key intermediate is proposed.