Year: 2026
Type: preprint
Abstract: 2 ABSTRACT: Reductive deoxygenation of benzylic alcohols is a valuable transformation that yields alkylated aromatic compounds. Even though hydroxyl group in these substrates is considered as activated, general mild methods for their reduction remain elusive. While many existing protocols require acidic reagents or additives detrimental for functional groups, milder alternatives are efficient only with 1° benzylic alcohols and diarylmethanols. Here we report that low-valent titanium alkoxides promote deoxygenation of 1°, 2° and 3° benzylic alcohols under basic conditions compatible with acetal, alkene, ester, amide, nitrile, aryl halides and benzyloxy groups. The low-valent titanium reagents were generated in situ by the reduction of Ti(OiPr)4 either with a dihydrobenzimidazol derivative under irradiation with blue light or with pieces of sodium metal. Mechanistic studies revealed that the deoxygenation step is promoted by Ti(III) alkoxides, while OH-groups of the substrate serve as a source of H-atoms.
Source: ChemRxiv
Institutions: Belarusian State University, Anti-Doping Laboratory
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7220694149