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The control of stereo-, regio-, and chemo-selectivity in transition-metal-catalyzed coupling reactions is a key topic in organic synthesis. Several methods for controlling selectivity have been reported thus far. On the other hand, the reduction of catalyst loading during reactions is one of the most important issues in organic synthesis from the standpoint of green sustainable chemistry. As another advantage of reducing catalyst loading, the expression of reaction selectivity and the substituent effect caused by the reduction of catalyst loading to the parts-per-million (ppm) level in various catalytic reactions is presented herein.