Chapter 11
Selective Hydrogenation of Aldehydes
and Ketones
Israel Cano and Piet W. N. M. van Leeuwen
Abstract The selective hydrogenation of α,β-unsaturated aldehydes and ketones
catalyzed by metal nanoparticles is reviewed with an emphasis on the recent advances
in this area. Key issue is the selectivity for allyl alcohol formation. General trends in
the use of conditions, ligands and co-catalysts were observed. In spite of the progress
achieved in the last two decades, there is still a quest for cost-effective, selective and
fast new catalysts.
Keywords Chemoselective hydrogenation · Metal nanoparticles · α,β-unsaturated
carbonyl compounds · Unsaturated aldehydes · Unsaturated ketones · Unsaturated
alcohol · Au NPs · Lewis acids · Oxide supports · Heterolytic cleavage of H 2
11.1 Introduction
Selective hydrogenation of α,β-unsaturated aldehydes and ketones has been a longstanding theme in catalysis as it is scientifically interesting which function will be
hydrogenated, but also because partial hydrogenation is of industrial importance.
The target molecule is usually the allylic alcohol, as the other half-product, the
saturated aldehyde or ketone, is thermodynamically more stable than the former and
via isomerization one can always arrive at full selectivity to the saturated aldehyde or
ketone (Scheme 11.1). In terms of selectivity, therefore, the product of most interest
is the unsaturated alcohol. High selectivity to the allyl alcohol at high conversion
requires that all rates of reaction in Scheme 11.1 are very low except the one that
leads to allyl alcohol. All five steps are very common and straightforward.
I. Cano (B)
Departamento de Física Aplicada, Facultad de Ciencias, Universidad de Cantabria,
39005 Santander, Spain
e-mail: israel.canorico@unican.es
P. W. N. M. van Leeuwen
LPCNO, Institut National des Sciences Appliquées-Toulouse,
135 Avenue de Rangueil, Toulouse 31077, France
e-mail: vanleeuw@insa-toulouse.fr
© Springer Nature Switzerland AG 2020
P. W. N. M. van Leeuwen and C. Claver (eds.), Recent Advances in Nanoparticle Catalysis,
Molecular Catalysis 1, https://doi.org/10.1007/978-3-030-45823-2_11
345
Selective Hydrogenation of Aldehydes
and Ketones
Israel Cano and Piet W. N. M. van Leeuwen
Abstract The selective hydrogenation of α,β-unsaturated aldehydes and ketones
catalyzed by metal nanoparticles is reviewed with an emphasis on the recent advances
in this area. Key issue is the selectivity for allyl alcohol formation. General trends in
the use of conditions, ligands and co-catalysts were observed. In spite of the progress
achieved in the last two decades, there is still a quest for cost-effective, selective and
fast new catalysts.
Keywords Chemoselective hydrogenation · Metal nanoparticles · α,β-unsaturated
carbonyl compounds · Unsaturated aldehydes · Unsaturated ketones · Unsaturated
alcohol · Au NPs · Lewis acids · Oxide supports · Heterolytic cleavage of H 2
11.1 Introduction
Selective hydrogenation of α,β-unsaturated aldehydes and ketones has been a longstanding theme in catalysis as it is scientifically interesting which function will be
hydrogenated, but also because partial hydrogenation is of industrial importance.
The target molecule is usually the allylic alcohol, as the other half-product, the
saturated aldehyde or ketone, is thermodynamically more stable than the former and
via isomerization one can always arrive at full selectivity to the saturated aldehyde or
ketone (Scheme 11.1). In terms of selectivity, therefore, the product of most interest
is the unsaturated alcohol. High selectivity to the allyl alcohol at high conversion
requires that all rates of reaction in Scheme 11.1 are very low except the one that
leads to allyl alcohol. All five steps are very common and straightforward.
I. Cano (B)
Departamento de Física Aplicada, Facultad de Ciencias, Universidad de Cantabria,
39005 Santander, Spain
e-mail: israel.canorico@unican.es
P. W. N. M. van Leeuwen
LPCNO, Institut National des Sciences Appliquées-Toulouse,
135 Avenue de Rangueil, Toulouse 31077, France
e-mail: vanleeuw@insa-toulouse.fr
© Springer Nature Switzerland AG 2020
P. W. N. M. van Leeuwen and C. Claver (eds.), Recent Advances in Nanoparticle Catalysis,
Molecular Catalysis 1, https://doi.org/10.1007/978-3-030-45823-2_11
345