Aldehyde-Catalyzed Transition Metal-Free Dehydrative β-Alkylation of Methyl Carbinols with Alcohols

作者: Qing Xu , Jianhui Chen , Quan Liu

DOI: 10.1002/ADSC.201200996

关键词: Borrowing hydrogenAldol condensationChemistryAlcoholAlkylationCatalysisAlcohol oxidationAldehydeOppenauer oxidationOrganic chemistry

摘要: Different to the borrowing hydrogen strategy in which alcohols were activated by transition metal-catalyzed anaerobic dehydrogenation, direct addition of aldehydes was found be an effective but simpler way alcohol activation that can lead efficient and green aldehyde-catalyzed metal-free dehydrative C-alkylation methyl carbinols with alcohols. Mechanistic studies revealed reaction proceeds via situ formation ketones Oppenauer oxidation external aldehydes, aldol condensation, Meerwein–Ponndorf–Verley (MPV)-type reduction α,β-unsatutated substrate alcohols, affording useful long chain generating as by-products will recovered next condensation finish catalytic cycle.

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