Abstract:
Transition metal catalyzed selective C-C, C-N and C-0 bond activation reactions
are fundamentally important in organometallic chemistry and organic synthesis. Catalytic
C-C, C-N and C-0 activation are highly valuable for reforming processes of crude oils.
Significant research has been devoted to transition metal mediated C-C, C-N and C-0 bond
cleavage reactions to form new compounds as these processes are expected to provide
novel ways to transformation of inexpensive hydrocarbons into more commercially
valuable products such as pharmaceuticals, agrochemicals and polymers.
A few examples of transition metal catalyzed cross coupling reactions involving CN
bond cleavage have been reported. A well-defined Ru catalytic system has been
developed for oxidative alkylation of alcohol by deaminative coupling reactions of amines
to form alkylated ketones. The catalytic method was successfully applied to the
decarboxylative and deaminative coupling of amino acids with ketones.
Reductive deoxygenation of aldehydes and ketones has attracted considerable
attention due to its many applications in fine-chemical synthesis and biofuel production.
Classical methods for the deoxygenation of carbonyl compounds are generally associated
with harsh reaction conditions and the use of stoichiometric amounts of toxic reagents, and
poor functional-group tolerance. A well-defined Ru-H catalyst was found to mediate the
reductive deoxygenation of carbonyl compounds to produce aliphatic compounds. Two
different mechanistic pathways have been investigated in detail to probe the electronic
nature of the catalysts and ligands.
Reductive etherification of ketones/aldehydes and alcohols have been studied
intensively as cheaper and greener ways to synthesize ethers. A method for the reductive
coupling of carbonyl compounds with alcohols has been developed, which involved a
highly chemoselective formation of unsymmetrically substituted ether products. The
catalytic etherification method employs cheaply available molecular hydrogen as the
reducing agent, tolerates a number of common functional groups, and uses environmentally
benign water as the solvent.
