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The, ee in non-Curtin-Hammett conditions was estimated as follows: First, the percentage of the reaction going through the reaction channels that lead to syn and anti carbene intermediates was calculated on the basis of the relative energies of TS 8 c. Next, and considering that the ester rotation is faster than the carbene addition to ethylene, the percentage of the reaction going through the Re and Si reaction channels was calculated separately for the syn and anti reaction channels on the basis of the relative energies of TSs 10c-svn and 10c-anti. Finally, the percentage of R and S products, and hence the enantioselectivity, was estimated from the above percentages. For instance, in the case of the E0+ ZPE energies, 37.6, of the reaction occurs through the syn reaction channel and 62.4% through the and reaction channel. 100% of the syn carbene intermediates give the R product, whereas on
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0+ ZPE energies, 37.6 % of the reaction occurs through the syn reaction channel and 62.4% through the and reaction channel. 100% of the syn carbene intermediates give the R product, whereas only 34.6% of the anti carbene intermediates give the R product. This allows an estimate of 0.376×1.00+0.624×0.346 = 0.592 (ca. 59%) for the R product, and hence 18% ee.
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