Consistent with the Curtin–Hammett principle, the ratio of products depends on the absolute energetic barrier of the irreversible step of the reaction, and does not reflect the equilibrium distribution of substrate conformers. The relative free energy profile of one example of the Noyori asymmetric hydrogenation is shown below: Enantioselective lithiation Dynamic kinetic resolution under Curtin–Hammett conditions has also been applied to enantioselective lithiation reactions. In the reaction below, it was observed that product enantioselectivities were independent of the chirality of the starting material. The use of (−)-sparteine is essential to enantioselectivity, with racemic product being formed in its absence. Equilibration between the two alkyllithium complexes was demonstrated by the observation that enantioselectivity remained constant over the course of the reaction. Were the two reactant complexes not rapidly interconverting, enantioselectivity would erode over time as the faster-reacting conformer was depleted. Application to regioselective acylation The Curtin–Hammett principle has been invoked to explain regioselectivity in the acylation of 1,2-diols. Ordinarily, the less-hindered site of an asymmetric 1,2-diol would experience more rapid esterification due to reduced steric hindrance between the diol and the acylating reagent. Developing a selective esterification of the most substituted hydroxyl group is a useful transformation in synthetic organic chemistry, particularly in the synthesis of carbohydrates and other polyhdyroxylated compounds. Stannylene acetals have been used to efficiently achieve this transformation. The asymmetric diol is first treated with a tin reagent to produce the dibutylstannylene acetal. This compound is then treated with one equivalent of acyl chloride to produce the stannyl monoester. Two isomers of the stannyl ester are accessible, and can undergo rapid interconversion through a tetrahedral intermediate. Initially, the less stable isomer predominates, as it is formed more quickly from the stannyl acetal. However, allowing the two isomers to equilibrate results in an excess of the more stable primary alkoxystannane in solution. The reaction is then quenched irreversibly, with the less hindered primary alkoxystannane reacting more rapidly. This results in selective production of the more-substituted monoester. This is a Curtin–Hammett scenario in which the more stable isomer also reacts more rapidly. Application to asymmetric epoxidation The epoxidation of asymmetric alkenes has also been studied as an example of Curtin–Hammett kinetics. In a computational study of the diastereoselective epoxidation of chiral allylic alcohols by titanium peroxy complexes, the computed difference in transition state energies between the two conformers was 1.43 kcal/mol. Experimentally, the observed product ratio was 91:9 in favor