Transfer hydrogenation of ketones

The asymmetric transfer hydrogenation of ketones represents an alternative to 

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Table 2 Results of the transfer hydrogenation of ketones with fluorinated (salen)Ir complexes under biphasic conditions ...

On the other hand, one of the first chiral sulfur-containing ligands employed in the asymmetric transfer hydrogenation of ketones was introduced by Noyori el al Thus, the use of A-tosyl-l,2-diphenylethylenediamine (TsDPEN) in combination with ruthenium for the reduction of various aromatic ketones in the presence of i-PrOH as the hydrogen donor, allowed the corresponding alcohols to be obtained in both excellent yields and enantioselectivities, as... 

The use of chiral ruthenium catalysts can hydrogenate ketones asymmetrically in water. The introduction of surfactants into a water-soluble Ru(II)-catalyzed asymmetric transfer hydrogenation of ketones led to an increase of the catalytic activity and reusability compared to the catalytic systems without surfactants.8 Water-soluble chiral ruthenium complexes with a (i-cyclodextrin unit can catalyze the reduction of aliphatic ketones with high enantiomeric excess and in good-to-excellent yields in the presence of sodium formate (Eq. 8.3).9 The high level of enantioselectivity observed was attributed to the preorganization of the substrates in the hydrophobic cavity of (t-cyclodextrin. 

Noyori and coworkers reported well-defined ruthenium(II) catalyst systems of the type RuH( 76-arene)(NH2CHPhCHPhNTs) for the asymmetric transfer hydrogenation of ketones and imines [94]. These also act via an outer-sphere hydride transfer mechanism shown in Scheme 3.12. The hydride transfer from ruthenium and proton transfer from the amino group to the C=0 bond of a ketone or C=N bond of an imine produces the alcohol or amine product, respectively. The amido complex that is produced is unreactive to H2 (except at high pressures), but readily reacts with iPrOH or formate to regenerate the hydride catalyst. 

Palmer and Wills in 1999 reviewed other ruthenium catalysts for the asymmetric transfer hydrogenation of ketones and imines [101]. Gladiali and Mestro-ni reviewed the use of such catalysts in organic synthesis up to 1998 [102]. Review articles that include the use of ruthenium asymmetric hydrogenation catalysts cover the literature from 1981 to 1994 [103, 104], the major contributions... 

Fig. 15.10 Transfer hydrogenation of ketones at 80°C catalyzed by [RhCI(COD)]2/TPPTS. Values shown in brackets are yields (TOF, hf1).

Evans et al.106 report an asymmetric transfer hydrogenation of ketones using samarium(III) complex (108) as the catalyst at ambient temperature in 2-propanol. The products showed ee comparable with those obtained through enantioselective borane reduction (Scheme 6-48). 

Figure 9.2 Transfer hydrogenation of ketones catalyzed by Ru(II)(2-azanorbornyl-methanol) complexes.

Palmer, M.J., Kenny, J.A., Walsgrove, T., Kawamoto, A.M. and Wills, M., Asymmetric transfer hydrogenation of ketones using amino alcohol and monotosylated diamine derivatives of indane. 

There have been many reports of the use of iridium-catalyzed transfer hydrogenation of carbonyl compounds, and this section focuses on more recent examples where the control of enantioselectivity is not considered. In particular, recent interest has been in the use of iridium A -heterocyclic carbene complexes as active catalysts for transfer hydrogenation. However, alternative iridium complexes are effective catalysts [1, 2] and the air-stable complex 1 has been shown to be exceptionally active for the transfer hydrogenation of ketones [3]. For example, acetophenone 2 was converted into the corresponding alcohol 3 using only 0.001 mol% of this... 

The same catalyst has also been used for the reduction of aldehydes to primary alcohols [7]. Several other iridium W-heterocyclic carbene complexes have been shown to be successful as catalysts for the transfer hydrogenation of ketones [8-12], including the interesting complex 6, where the cyclopentadienyl ring is tethered to the 77-heterocyclic carbene. Complex 6 was employed at low catalyst loading for the reduction of a range of ketones including the conversion of cyclohexanone 11 into cyclohexanol 12 [13]. 

I 5 Catalytic Activity of Cp Iridium Complexes in Hydrogen Transfer Reactions Table 5.3 Transfer hydrogenation of ketones and imines catalyzed by ll. "... 

Figure 1.23. Asymmetric transfer hydrogenation of ketones catalyzed by chiral arene-Ru...

Figure 1.25 exemplifies the strucmres of certain efficient precatalysts for asymmetric transfer hydrogenation of ketones. Precatalysts C1-C3 use the NH effect described above. A turnover frequency, defined as moles of product per mol of catalyst per hour, of 30,000 h is achieved by using of C2 and an alkaline base in 2-propanol. A Rh complex C3 is an isolobal to the corresponding arene-Ru complex (see Figure 1.23). The Ru complexes C4 " and C5 without NH group in ligand catalyze the reaction by different mechanisms. A higher than 90% optical yield is achieved by using C5 in reduction of certain aliphatic ketones.

Inspired by the reaction mechanism of Noyori s catalytic enantioslective transfer hydrogenation of ketones (32) using a chiral Ru-amido complex 31, Dcariya et al. reported that 31 can also function as a unique Bronsted base-Bronsted acid catalyst... 

TABLE 9.37. BIS(OXAZOLINE)-MEDIATED TRANSFER HYDROGENATION OF KETONES... 

Transfer hydrogenation of ketones using metal complexes with a chiral water-soluble [97,98] and a dendritic ligand [99] was investigated for use in recycling catalysts. The reaction with immobilized catalysts has also been reported [100]. 

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