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The chiral titanium complex-catalyzed ene-type reaction and the Mukaiyama aldol reaction with fluoral are shown as an efficient route to the enantioselective and diastereo-selective synthesis of CF3-substituted compounds of biological and synthetic importance. The ene reactivity of trihaloaldehydes including acetaldehyde has been analyzed in terms of the balance of LUMO energy level and the electron density on the carbonyl-carbon on the basis of analysis using the semi-empirical techniques (MNDO, AM1, and PM3) and ab initio (HF/6-31G**) methods.

