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Aldehyde‐Catalyzed Transition Metal‐Free Dehydrative β ‐ Alkylation of Methyl Carbinols with Alcohols
Author(s) -
Xu Qing,
Chen Jianhui,
Liu Quan
Publication year - 2013
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201200996
Subject(s) - chemistry , aldehyde , dehydrogenation , catalysis , alkylation , transition metal , alcohol , aldol condensation , organic chemistry , condensation , aldol reaction , alcohol oxidation , substrate (aquarium) , physics , thermodynamics , oceanography , geology
Different to the borrowing hydrogen strategy in which alcohols were activated by transition metal‐catalyzed anaerobic dehydrogenation, the direct addition of aldehydes was found to be an effective but simpler way of alcohol activation that can lead to efficient and green aldehyde‐catalyzed transition metal‐free dehydrative C‐ alkylation of methyl carbinols with alcohols. Mechanistic studies revealed that the reaction proceeds via in situ formation of ketones by Oppenauer oxidation of the methyl carbinols by external aldehydes, aldol condensation, and Meerwein–Ponndorf–Verley (MPV)‐type reduction of α,β‐unsatutated ketones by substrate alcohols, affording the useful long chain alcohols and generating aldehydes and ketones as the by‐products that will be recovered in the next condensation to finish the catalytic cycle.