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2D free-energy contour map for the 1st methylation on Nη1. Rx: the reaction coordinate of the methyl transfer; Ry: the reaction coordinate for the proton transfer. Points A, B, and D designate the reactant, near transition state, and product complexes, respectively. Some contour lines are shown with respective energy values. The energy barrier is estimated to be around 19–20 kcal/mol.
