Formic acid and formates
Deprotonated formic acid splits into hydride and CO2, wherefore it works as a reducing agent.
> Formic acid as an oxidizing agent.
Name Reactions
Reactions
Recent Literature
In a biphasic reaction media for the asymmetric biocatalytic reduction of
ketones with in situ cofactor regeneration, both enzymes (ADH
and FDH) remain stable. Reductions with poorly
water-soluble ketones were carried out at substrate concentrations of > 10 mM,
and alcohols were formed with good conversions in high enantioselectivity.
H. Groeger, W. Hummel, S. Buchholz, K. Drauz, T. V. Nguyen, C. Rollmann, H. Huesken, K. Abokitse, Org. Lett., 2003, 5, 173-176.
An on-water Ir(III)-diamine catalysis represents an efficient, simple and
environmentally friendly catalytic system for the transfer hydrogenation of
aldehydes. The catalyst tolerates various synthetically useful groups
including nitro groups, halogens, ketones, esters and olefins.
X. Wu, J. Liu, X. Li, A. Zanotti-Gerosa, F. Hancock, D. Vinci, J. Ruan, J. Xiao, Angew. Chem. Int. Ed., 2006, 45, 6717-6722.
Asymmetric transfer
hydrogenation of various simple aromatic ketones by the Ru-TsDPEN
catalyst was shown to be feasible in aqueous HCOONa without calling for
any catalyst modification, furnishing ee's of up to 95% and
significantly faster rates than in the HCOOH-NEt3 azeotrope.
X. Wu, X. Li, W. Hems, F. King, J. Xiao, Org. Biomol. Chem., 2004, 2, 1818-1821.
Pd/P(t-Bu)3 is an efficient and mild catalyst for selective
reduction of various alkenes under transfer-hydrogenation conditions leading to
the corresponding saturated derivatives in good yields.
J. M. Brunel, Synlett, 2007, 330-332.
Various carbon-carbon double bonds in olefins and α,β-unsaturated ketones
were effectively reduced to the corresponding alkanes and saturated ketones,
using ammonium formate as a hydrogen transfer agent in the presence of Pd/C
as catalyst in refluxing methanol.
Z. Paryzek, H. Koenig, B. Tabacka, Synthesis, 2003, 2023-2026.
A microwave-assisted, palladium-catalyzed catalytic transfer hydrogenation of different homo- or heteronuclear
organic compounds using formate salts as a hydrogen source was performed in ([bmim][PF6]. Essentially pure products could be isolated in
moderate to excellent yields by simple liquid-liquid extraction.
H. Berthold, T. Schotten, H. Hönig, Synthesis, 2002, 1607-1610.
Nanopalladium particles supported on a amphiphilic polystyrene-poly(ethylene
glycol) resin catalyzed hydrogenation of olefins and hydrodechlorination of
chloroarenes under aqueous conditions.
R. Nakao, H. Rhee, Y. Uozumi, Org. Lett., 2005,
7, 163-165.
Various di- and triarylfurans were prepared in high yields from
but-2-ene-1,4-diones and but-2-yne-1,4-diones using formic acid in the
presence of a catalytic amount of palladium on carbon in poly(ethylene
glycol)-200 as solvent under microwave irradiation.
H. S. P. Rao, S. Jothilingam, J. Org. Chem., 2003, 68, 5392-5394.
Several aryl-substituted pyrrole derivates were prepared conveniently in a
microwave-assisted one pot-reaction from but-2-ene-1,4-diones and
but-2-yne-1,4-diones via Pd/C-catalyzed hydrogenation of the carbon-carbon
double bond/triple bond followed by amination-cyclization.
H. S. P. Rao, S. Jothilingam, H. W. Scheeren, Tetrahedron, 2004, 60, 1625-1630.
The synthesis of 3,5-dimethyl-N-nitro-1-pyrazole-1-carboxamidine (DMNPC) has been optimised. A detailed protocol for the preparation of a range of guanidines via nitroguanidines
is described using DMNPC as guanidinylating reagent.
J. A. Castillo-Meléndez, B. T. Golding, Synthesis,
2004, 1655-1663.
Amidines can be prepared by
reducing acylated amidoximes with potassium formate. This method has proved to
be very simple and effective.
K. Nadrah, M. Sollner Dolenc, Synlett, 2007,
1257-1258.
