Reduction of carbonyl compounds

Name Reactions

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.

The organic reductant 1-acetyl-2,3-dimethylimidazolidine is able to directly reduce a series of aromatic, aliphatic and α,β-unsaturated aldehydes as well as imines in high yields.
D. Li, Y. Zhang, G. Zhou, W. Guo, Synlett, 2008, 225-228.

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.

Red-Al is an efficient chelation-controlled reducing reagent for acyclic acetal-protected R-hydroxy ketones. Typically, high diastereomeric ratios and yields can be achieved for the synthesis of 1,2-anti-diols.
N. Bajwa, M. P. Jennings, J. Org. Chem., 2008, 73, 3638-3641.

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-C_n-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.

Related

The rhenium-catalyzed hydrosilation of aldehydes and ketones under ambient temperature and atmosphere gave protected alcohol as silyl ether in good yields. The mechanism is discussed.
E. A. Ison, E. R. Trivedi, R. A. Corbin, M. M. Abu-Omar, J. Am. Chem. Soc., 2005, 127, 15374-15375.

Optimizations to generate CuH in situ have led to an efficient and inexpensive hydrosilylation method for dialkyl ketones.
B. H. Lipshutz, C. C. Caires, P. Kuipers, W. Chrisman, Org. Lett., 2003, 5, 3085-3088.

Aliphatic carboxyl derivatives (acids, acyl chlorides, esters) and aldehydes were efficiently reduced to the methyl group by HSiEt₃ in the presence of catalytic amounts of B(C₆F₅)₃. Aromatic carboxylic acids, as well as other carbonyl functional equivalents, underwent smooth partial reduction to the corresponding TES-protected benzylic alcohols in competition with a Friedel-Crafts-like alkylation decreasing the overall selectivity of the reduction process.
V. Gevorgyan, M. Rubin, J.-X. Liu, Y. Yamamoto, J. Org. Chem, 2000, 66, 1672-1675.