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A weak base, CsOAc, promotes Suzuki–Miyaura crosscoupling and related Pdcatalyzed reactions under anhydrous conditions as effectively as stronger bases. Aryl triflates exhibit unusual reaction rates, which are comparable to that of bromoarenes. A neglected sixmembered transitionstate model was proposed to give alternative insight into the key process of transmetalation.© WileyVCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009

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