Ethers are commonly observed in pharma, agro, and fine chemicals as they impart desirable steric and electronic properties on them. It is therefore advantageous to have a robust synthesis of ethers from readily available materials. The direct conversion of an ester to ether is one such transformation. Esters are easily prepared by condensation reactions between acids and alcohols. The typical ester reduction proceeds through hydride addition to the carbonyl resulting in a tetrahedral acetal intermediate. Under normal conditions this acetal will collapse, ejecting the ether oxygen and resulting in an aldehyde or over-reduction to the alcohol. We will utilize the tetrahedral intermediate resulting from the reduction of an ester to chemoselectively generate an oxocarbenium ion that can be reduced to form an ether. This will demonstrate a non-traditional reactivity of esters that is similar to amide reduction to an amine. While this reaction has been explored in the literature, significant drawbacks include long reaction times, the inability to use aromatic esters, significant and unwanted side products, and/or low yields to form substituted ethers. Using <i>in-situ</i> ReactIR reaction monitoring to monitor disappearance of the ester carbonyl group in real time, we aim to define the variables for a predictable method for ester to ether conversion. We are also developing a one-pot strategy to form substituted ethers directly by introducing a nucleophile during the reaction.

Reductive conversion of acyclic esters to ethers using ReactIR

254th National Meeting (2017)

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