Selective Catalytic Synthesis of Unsymmetrical Ethers from the Dehydrative Etherification of Two Different Alcohols

The cationic ruthenium–hydride complex [(C₆H₆)­(PCy₃)­(CO)­RuH]⁺BF₄^– catalyzes selective etherification of two different alcohols to form unsymmetrically substituted ethers. The catalytic method exhibits a broad substrate scope while tolerating a range of heteroatom functional groups in forming unsymmetrical ethers, and it is successfully used to directly synthesize a number of highly functionalized chiral nonracemic ethers.