(655h) Selective C-C Bond Scission of Primary Alcohols Using Cerium Oxide-Supported Palladium Catalyst

Biomass
attracts significant attention as a carbon-neutral resource with the potential
to suppress the CO₂ emissions. Recently, the biomass-derived chemicals
such as glycerol, furfural, and levulinic acid are identified as the best
suited alternatives for petroleum-derived chemicals. From the stand point of
green sustainable chemistry, development of highly selective catalytic
transformation of these compounds to valuable chemicals has been desired. To
date, much effort has been devoted to selective C–O bond cleavage of high-oxygen
containing biogenic polyols, such as glycerol, to produce valuable chemicals by
hydrogenolysis and deoxydehydration.^1,2 On the other hand, C–C bond
cleavage has not yet been widely researched despite its great potential to
extend the utility of biomass-derived chemicals. The reported C–C bond cleavage
methods often suffer from low selectivity toward the desired chemicals and
limited substrate scope. In our group, we have reported the selective C–C bond
scission of platform biomass-derived chemicals catalyzed by Ru/CeO₂
in the presence of water under 3 MPa of H₂.³ In order to open
new routes for industrially important chemicals from a wide range of biomass
derivatives, development of highly selective and greener C–C bond scission
catalysts is desired.

In
this work, we found that cerium oxide-supported palladium (Pd/CeO₂)
efficiently promoted the selective one-carbon scission of primary alcohols under
air without H₂. The cleavage of C–C bonds occurs at positions adjacent
to the hydroxymethyl groups (Scheme 1). The solid catalyst was reusable without
appreciable loss of the activity and selectivity.

References

[1] T. Mizugaki, Y. Nagatsu, K. Togo, Z. Maeno, T.
Mitsudome, K. Jitsukawa, K. Kaneda, Green Chem. 2015, 17,
5136–5139.

[2] T. Mizugaki, K. Togo, Z. Maeno, T. Mitsudome, K.
Jitsukawa, K. Kaneda, ACS Sustainable Chem. Eng. 2016, 4,
682–685.

[3] T.
Mizugaki, K. Togo, Z. Maeno, T. Mitsudome, K. Jitsukawa, K. Kaneda, Sci.
Rep. 2017, 7, 14007.