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An efficient synergistic trityl cation ([Ph3C][B(C6F5)4])/triflic anhydride (Tf2O) catalyzed alkylation of phenols with alcohols is reported. Benefiting from the formation of the triflate in situ, cheap and readily available active alcohols can be used as the alkylating reagents, and the reaction proceeds under mild reaction conditions with a broad substrate scope. This protocol enables the synthesis of ortho-selective phenols and 2,4,6-trisubstitued phenols containing three different alkyl groups. tert-Amyl triflate was synthesized, and mechanistic studies support a triflate-mediated alkylation process.

In the presence of inorganic iodide, the methoxy CO bond in 2‐methoxyfurans may be cleaved to afford the corresponding lactonic anion. Due to the presence of an electron‐withdrawing group at the 3‐position, the alkylation with normal organic iodides occurred at the 3‐position highly regioselectively. However, when electron‐deficient allylic iodides with an electron‐withdrawing group at the 2‐position were used the 5‐alkylation products were formed as the major products with sodium iodide as the catalyst. With magnesium iodide as the catalyst, the 5‐allylation occurred highly regioselectively. As a whole, the 3‐ vs.5‐alkylation selectivity may be determined by the relative steric hindrance at the 3‐ and 5‐positions and the electronic effect of the allylic iodides. A rationale was proposed.

The regioselective synthesis of trisubstituted furans (II) is achieved via phosphine‐catalyzed ring‐opening cycloisomerization reactions of the functionalized cyclopropenyl carboxylates (I) with moderate to very good yields.