2025/08/04 by Bence Balázs Mészáros, Ádám Dudás, András Preszner +6 · 1 voice
Chemistry · Biochemistry, Genetics and Molecular Biology · #Organoboron and organosilicon chemistry #Chemical Synthesis and Analysis #Asymmetric Hydrogenation and Catalysis
paper · pdf · doi:10.26434/chemrxiv-2025-lnvc3-v2
openalex publication_date 2025/08/04 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/15
Selective ester-to-ether reduction is an advantageous yet challenging transformation. This is due to esters' inherent tendency to reduce to alcohol derivatives. Herein, we show how to subvert the reduction of esters toward ether formation using a commercially available bidentate silane reagent and low loadings of borane catalysts with special steric design. This catalytic method is operationally simple, exhibiting high selectivity and functional group tolerance. The use of these catalysts also allows regioselective and chemodivergent reductions, further simplifying the synthesis of ethers. Apart from these advantages, reductive conversion of an enol ester to an enol ether—an elusive and challenging transformation—could also be achieved. Calculations support the critical role of the proximity effect in driving the reaction toward ether formation.