The Critical Effect of the Countercation in the Direct Cupration of Fluoroform with [Cu(OR)2]−

Just a spectator or a key player? The alkali-metal counterion (K+) plays a remarkable key role in the recently discovered cupration reaction of fluoroform with dialkoxycuprates. A total of eight Lewis acid and Lewis base centers synergistically interacting with one another arrange in a stable transition state, providing a low-energy pathway for this unique transformation.