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The initially formed TCs for 11b and 11c are not completely symmetric regarding the orientation of the methoxy substituents. Symmetric, ca. 1 kcal/mol more stable TC structures are achieved through flipping one methoxy from the reactant to the product orientation via a small barrier of 1.4 (11b) or 0.4 kcal/mol (11c). Turning the other methoxy substituent also to the product orientation yields a TC that is equivalent to the initial one.
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33747787135
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3Cl is frozen to the geometry it adopts in the RC in which it is already slightly deformed with respect to its own equilibrium structure.
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52
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