Categories: O-H Bond Formation >
Reduction of carbonyl compounds
Name Reactions
Corey-Bakshi-Shibata Reduction
Meerwein-Ponndorf-Verley Reduction (MPV)
Recent Literature
Aryl ketones were reduced to the corresponding alcohols with excellent
enantioselectivity by trichlorosilane in the presence of a catalytic amount of
N-formyl-α'-(2,4,6-triethylphenyl)-L-proline as an activator.
Y. Matsumura, K. Ogura, Y. Kouchi, F. Iwasaki, O. Onomura, Org. Lett.,
2006, 8, 3789-3792.
The catalytic asymmetric borane reduction of both electron-deficient and
electron-rich ketones was achieved with high enantioselectivity with a C3-symmetric
chiral tris(β-hydroxy phosphoramide) ligand .
D.-M. Du, T. Fang, J. Xu, S.-W. Zhang, Org. Lett.,
2006, 8, 1327-1330.
A complex of CuH and Takasago's nonracemic ligand, DTBM-SEGPHOS, is an
especially reactive reagent for asymmetric hydrosilylation of heteroaromatic
ketones under very mild conditions. PMHS serves as an inexpensive source of
hydride for the in situ generation of CuH.
B. H. Lipshutz, A. Lower, K. Noson, Org. Lett.,
2002, 4, 4045-4048.
Decaborane was found to be an effective agent for the chemoselective
reduction of ketones to alcohols in the presence of pyrrolidine and cerium(III)
chloride heptahydrate in methanol.
J. W. Bae, S. H. Lee, Y. J. Jung, C.-O. Maing, C. M. Yoon, Tetrahedron Lett., 2001, 42, 2137-2139.
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.
An iron complex containing electronically coupled acidic and hydridic hydrogens
catalyzes the hydrogenation of ketones under mild conditions and shows high
chemoselectivity for aldehydes, ketones, and imines. Isolated carbon double and
triple bonds, aryl halides, nitrates, epoxides, and ester functions are
unaffected by the hydrogenation conditions.
C. P. Casey, H. Guan, J. Am. Chem. Soc., 2007,
129, 5816-5817.
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.
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.
Pincer-aryl ruthenium(II) complexes form active catalysts in the reduction of
ketones by hydrogen transfer in i PrOH using KOH as promoter. At a KOH/Ru
molar ratio of 20/1 only trace amounts of aldol products are formed. Under these
conditions, the σ Ru-C bond is stable and the [Ru(PCP)PPh3] fragment
is preserved.
P. Dani, T. Karlen, R. A. Gossage, S. Gladiali, G. van Koten, Angew.
Chem., 2000, 112, 759-761.
The reduction of ketones and
aldehydes with lanthanide metals (La, Ce, Sm, Yb) and a catalytic amount of
iodine (5 mol %) in iPrOH proceeded smoothly to produce the
corresponding alcohols as the major products in good yield, while in THF,
methanol, and ethanol the pinacols were mainly produced. The yields of
alcohols were improved most effectively by the use of Sm metal.
S.-I. Fukuzawa, N. Nakano, T. Saitoh, Eur. J.
Org. Chem., 2004, 2863-2867.
I. Ibrahem, A. Córdova, Angew. Chem. Int. Ed., 2006, 45, 1952-1956.
Optically pure C2-symmetrical cyclic amines were
efficiently synthesized from the corresponding diols obtained from an
enantioselective borohydride reduction of diketones in the presence of a chiral
β-ketoiminato cobalt(II) catalyst.
M. Sato, Y. Gunji, T. Ikeno, T. Yamada, Synthesis, 2004,
1434-1438.
Reduction of β-hydroxyketones by SmI2/H2O/Et3N
provided 1,3-diols in quantitative yields with no byproduct formation.
T. A. Davis, P. R. Chopade, G. Hilmersson, R. A. Flowers, Org. Lett., 2005, 7, 119-122.
A mild, enantioselective hydrosilylation of 3-oxo-3-arylpropionic acid
methyl or ethyl esters using axially chiral BINAM N-heterocyclic carbene (NHC)-Rh(III) complexes
as catalysts gave 3-hydroxy-3-arylpropionic acid
methyl or ethyl esters in good yields with good to excellent
enantioselectivities under mild conditions.
. Xu, X. Gu, S. Liu, Q. Duo, M. Shi, J. Org. Chem., 2007,
72, 2240-2242.
An asymmetric α-alkylative reduction of prochiral ketones with primary
alcohols has been disclosed. The reaction is catalyzed by both iridium and
ruthenium complexes and gave optically active alcohols with elongation of
the carbon skeleton with high enantioselectivity.
G. Onodera, Y. Nishibayashi, S. Uemura, Angew. Chem. Int. Ed., 2006, 45, 3819-3822.
(R)-β-Hydroxy nitriles were obtained via a reduction catalyzed by a
recombinant carbonyl reductase with excellent optical purity and were further
converted to (R)-β-hydroxy carboxylic acids via a nitrilase-catalyzed
hydrolysis. The present study allows ready access to both chiral β-hydroxy
nitriles and β-hydroxy carboxylic acids of pharmaceutical importance.
D. Zhu, H. Ankati, C. Mukherjee, Y. Yang, E. R. Biehl, L. Hua, Org. Lett., 2007,
9, 2561-2563.
Various enantiomerically pure α-hydroxy esters were synthesized by a Ru-Cn-Tunephos-catalyzed
asymmetric hydrogenation of α-keto esters. High enantiomeric excess has been
achieved for both α-aryl and α-alkyl substituted α-keto esters.
C.-J. Wang, X. Sun, X. Zhang, Synlett,
2006, 1169-1172.
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