Fajar Firstya Adam

02211850010006
Teknik Reaksi Kimia Lanjutan (Program Pascasarjana)
REVIEW

Catalytic Transfer Hydrogenation

Transformation of organic synthesis compounds or biomass derived compounds often deal

with complicated structure of polyfunctional groups of its molecules. One of significant method and
interesting in practical research is examining Catalytic Transfer Hydrogenation reaction which
promising a new pathway of chemical conversion in especially reductive reaction techniques
eventhough this idea have been proposed and recently this issue, somehow revived. This techniques
provide of utilization of H atom bond scission from other hydrogen source rather than using
molecular hydrogen gaseous phase. Some disadvantages of using pressurized hydrogen is easily
ignited moreover in industrial large scale which may be took a huge risks. Along with Green
Chemistry terminology, a philosophy of chemical research engineering which lately discussed in
much publication then promotes the optimization of designing process with reducing of harmful
hazardous substance. Then, with those drawback mentioned earlier, the catalytic transfer
hydrogenation techniques should be considered. This technique used for reduction of unsaturated
organic compound with the aid of hydrogen source in a present of catalyst. Catalyst could be
homogenous or heterogenous. The mechanism of catalytic transfer hydrogenation can occur
according to two mechanism, hydricidic route which assisted by transition-metals or direct
hydrogen transfer by non-transition metals. Hydrogen source often utilize a solvent which can
release hydrogen or donoring its hydrogen most of solvent which can produce is organic solvent,
but anorganic compound, hydrazine should be an alternative. Essentially, the kinetics and rate of
catalytic transfer hydrogenation reaction affected by mostly, the nature of donor and solvent, which
the origin of hydrogen molecule, whereas in reductive reaction with pressurized hydrogen, the
pressure of hydrogen gases play the key role. Organic compound which suitable for hydrogen
donor, should have a very low oxidating potential, high reactivity, its interaction with catalyst and
sufficient of solubility with reactant. Mostly, unstaturated alcohol or short-chain alcohol often used
as hydrogen source because, not only as solvent but also as hydrogen donor another solvent could
inhibit transfer reaction, with aldehid group such as nitrobenzaldehid. Another variable which very
critical for reaction is temperature. Hydrogen transfer from donor to acceptor occurs in a high
temperature, but it can be lowered about 50% thanks to the present of metal catalyst which provide
this reaction at mild condition. And the last variables which truly determine the reaction is catalyst,
because, in the catalyst, providing a space where hydrogen transfer reaction took place. Not only
hydrogen transfer but also intermediate product such as formation of metal-hydride, rearrangement
of dehydrogenation of donor molecules on metal catalyst site, its stereochemical, how transfer
would be affected to the acceptor, including several scission of functional groups from donor and
acceptor, can be determine how mechanism should be occurred, and all of these phenomenon
should be specifically revealed to give a better selectivity from catalytic transfer hydrogenation
reaction on several organic substances. Application of these technique path in kinetic engineering
have been used for transformation several substances, depends on its target compound, for example,
reduction of double bond such as olefin, acetylene, and carbonyl compound, hydrogenolysys
reaction for nitil, halide and amine compound. Recently this technique applied in degradation or
transformation of complex substance such as lignin, glycerol or starch. By the end of this review
and information, hopefully this technique can be explored for further development, research and
study based this idea shoud be conducted and revisited.
Keyword : Hydrogen donor, Catalytic Transfer Hydrogenation, Organic Transformation, Catalyst
Fajar Firstya Adam
02211850010006
Teknik Reaksi Kimia Lanjutan (Program Pascasarjana)

Further Information and Cited publication,

Musolino, M.G., Scarpino, L.A., Maurellio, F., Pietropaolo, R (2009). "Selective Transfer
Hydrogenolysis promoted by supported Palladium Catalys in the absence of Hydrogen" Green
Chem 2009 11, (153-158)
Gilkey, M.J., B. Xu (2016) " Heterogeneous catalytic transfer hydrogenation as an effective
pathway in biomass upgrading". ACS Catalysis. 2016, 6, 1420−1436
Wang, D., Didier A (2015) " The Golden age of Transfer Hydrogenation". Chem. Review 2015,
115: (6621−6686)
Wang, J ., R Nie, L Xu, X Lyu, X Lu (2019) " Catalytic transfer hydrogenation of oleic acid to
octadecanol over magnetic recoverable cobalt catalysts". Green Chem 2019 2: (6621−6686)
Wolfson, A., I Grinberg, D Tavor (2019) " Solvent Selection in Transfer Hydrogenation and Suzuki
Cross-coupling ". Energy and Environmental Engineering 2013 1: (17-23)
Zhang, J (2018) " Catalytic transfer hydrogenolysis as an efficient route in cleavage of lignin and
model compounds". Green Energy & Environment 2018 3: (328-334)
Johnstone, R. A. W., Wilby, A. H., (1985) " Heterogeneous Catalytic Transfer Hydrogenation and
Its Relation to Other Methods for Reduction of Organic Compounds". Chem. Rev. 1985, 85,
(129-170)
Johnstone, R. A. W., Wilby, A. H., (1981) “Metal-assisted reactions part 10”. Tetrahedron 1981,
37,3667–3670.
Gandarias, I., P.L.Arias J. Requies M. El Doukkali M.B.Güemez (2011). "Liquid Phase Glycerol
Hydrogenolysis, to 1,2-Propanediol under nitrogen pressure using 2-propanol as Hydrogen
Source". Journal of Catalyst 282 (2011) 237-247