Reductive Deoxygenation of Benzylic Alcohols by Low-Valent Titanium Alkoxides
- 1Republican Scientific Center of Human Issues, Belarusian State University, Kurčatava 7, Minsk, Belarus, 220064
- 2National Anti-Doping Laboratory
- 3Scientific Testing Center Campilab Ltd., Centraĺnaja 30A, Dynaraŭka, Belarus, 222202
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.
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BibTeX
@misc{atroshchanka2026reductive,
title = {{Reductive Deoxygenation of Benzylic Alcohols by Low-Valent Titanium Alkoxides}},
author = {Dziyana Atroshchanka and Yahor Rusakovich and Antanina Shtytsko and Mark Senkevich and Gleb Kakouka and Vitaly Syakhovich and Alaksiej Hurski},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15009976/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009976/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Reductive Deoxygenation of Benzylic Alcohols by Low-Valent Titanium Alkoxides
AU - Dziyana Atroshchanka
AU - Yahor Rusakovich
AU - Antanina Shtytsko
AU - Mark Senkevich
AU - Gleb Kakouka
AU - Vitaly Syakhovich
AU - Alaksiej Hurski
PY - 2026
DA - 2026/10/06
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009976/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009976/v1
AB - 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.
ER -