Secondary alcohols (carbinols) react with
primary alcohols in dioxane at 80 °C in the presence of
a catalytic amount of RuCl2(PPh3)3 and KOH along with
a sacrificial hydrogen acceptor to afford the corresponding coupled secondary alcohols. The reaction is applicable to a wide range of aryl methyl, alkyl methyl,
and cyclic carbinols, and with alkyl methyl carbinols,
the alkylation took place exclusively at the less-hindered
methyl position over β-methylene and -methine.
A new reaction: A ruthenium‐catalyzed transfer of an alkyl group from a trialkylamine to the α‐carbon atom of a ketone leads in good yields to α‐alkylated ketones [Eq. (1)]. The reaction is applicable to a wide range of alkyl(alkyl), alkyl(aryl), and cyclic ketones, and in the case of unsymmetrical ketones it takes place regioselectively at the less hindered α‐position.
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