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Ethers are among the most important chemicals in organic synthesis, the pharmaceutical industry, agrochemical production, and material science. C–O bond formation via substitution is one of the most widely used strategies for ether formation. However, known methods usually employ transition-metal and bases to facilitate the process. In this work, we describe the base- and transition-metal-free ether formation via alcohol and phenol-participated substitution. The protocol allows access to a large number of ethers with enyne functional moieties, and features mild reaction conditions, high efficiency, and good regio- and stereoselectivities. The reaction could be readily scaled up, and the products could be used in a range of further transformations.

Two types of unprecedented organic phosphine-catalyzed trifunc-tionalization of ynones have been achieved under mild and environmentally benign conditions using iPrOH as the solvent, delivering a range of synthetically valuable acyloxy allylidene malonates and γ-alkylidenebutenolides in good yields with high stereoselectivities. A series of uncommon bond cleavage and bond formation processes have been observed in the reactions, showing the robustness of organocatalysis in facilitating complicated transformations. Mechanistic studies indicate that iPrOH plays a dual role as both the solvent and the reactant. [ABSTRACT FROM AUTHOR]