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

Abstract

The cationic ruthenium−hydride complex [(C 6 H 6 )(PCy 3 )(CO)RuH] + BF 4 − 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.

Synthesis of Biomass‐Derived Ethers for Use as Fuels and Lubricants

“…Another promising approach, particularly for the synthesis of asymmetrical ethers via direct etherification, is the use of so-called "heterogenized" homogeneous acid catalysts.F or example, the homogeneous cationic ruthenium-hydride complex [(C 6 H 6 )(PCy 3 )(CO)RuH] + BF 4 À (PCy 3 = tricyclohexylphosphine) is known to catalyzet he selective etherifi-cation of two different alcohols to form asymmetrical substituted ethers with al arges cope of substrates and without the need for reactive reagents or protecting groups. [167] Developing heterogeneous catalystst hat enables electivea symmetrical ether synthesis without the need for reductive etherification could lower costs associated with operating under hydrogen pressure and would allow more flexibility in the choice of alcohol substrates.…”

Synthesis of Symmetric and Unsymmetric Secondary Amines from the Ligand-Promoted Ruthenium-Catalyzed Deaminative Coupling Reaction of Primary Amines

“…17 Since these coupling reactions are driven by the formation of water, we reasoned that the analogous deaminative coupling reactions of amines could be achieved, where the formation of ammonia would serve as the driving force for such coupling reactions. Herein, we report the synthesis of symmetric and unsymmetric secondary amines from the catalytic deaminative coupling of primary amines.…”

Intermolecular Markovnikov-Selective Hydroacylation of Olefins Catalyzed by a Cationic Ruthenium–Hydride Complex

“…10 In an effort to extend the scope of C–H acylation of phenol and related arenes, 11 we have been exploring the coupling reaction of aldehydes with olefin substrates. Herein, we disclose a highly Markovnikov-selective intermolecular hydroacylation of aryl-substituted olefins to yield branched ketone products.…”