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Iridium-catalyzed carbonylations effect

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... [Pg.78]

FIGURE 4 Effect of additive concentration on rate of iridium-catalyzed methanol carbonylation (190 °C, 22 bar, 1950 ppm Ir). Adapted with permission from Figure 2 in reference [125], copyright 2004, American Chemical Society. [Pg.26]

Spogliarich et al. published the details of a study [15] on the electronic effect implicated in reactions catalyzed by iridium/phosphine systems, and found there to be a slight dependence on the charge distribution around the carbonyl group of the substrates, while electron-withdrawing groups enhance the reduction rate... [Pg.58]

Iridium nanopartides also catalyze the hydrogenation of benzyhnethylketone, with high selectivity in reduction of the aromatic ring (92% selectivity in saturated ketone, 8% in saturated alcohol at 97% benzylmethylketone conversion). This preferential coordination of the aromatic ring can be attributed to steric effects that make carbonyl coordination difficult. Therefore, metallic iridium nanoparticles prepared in ILs may serve as active catalysts for the hydrogenation of carbonyl compounds in both solventless and biphasic conditions. [Pg.387]

The major drawback in the development of efficient catalytic PK protocols is the use of carbon monoxide. Many groups probably refuse to use this reaction in their synthetic plans in order to avoid the manipulation of such a highly toxic gas. Carbonylation reactions without the use of carbon monoxide would make them more desirable and would lead to further advances in those areas. Once the use of rhodium complexes was introduced in catalytic PKR, two independent groups realized these species were known for effecting decarbonylation reactions in aldehydes, which is a way to synthesize metal carbonyls. Thus, aldehydes could be used as a source of CO for the PKR. This elegant approach begins with decarbonylation of an aldehyde and transfer of the CO to the enyne catalyzed by rhodium, ruthenium or iridium complexes under argon atmosphere (Scheme 36). [Pg.232]

The diphosphine complexes [Ir(dppe)2]+ and [Ir(dppe)(cod)]+ reportedly catalyze the decar--bonylation of aldehydes.504,505 Methanol carbonylation is catalyzed by lr(Cl)4]-H20 to yield acetic acid. The active species is thought to be an acetyl iridium(III) species, wherein the rate-determining step involves electrophilic attack of this species on methanol. The effects of added iodide ion on reaction rates have also been investigated.506... [Pg.1160]

A process for the coproduction of acetic anhydride and acetic acid, which has been operated by BP Chemicals since 1988, uses a quaternary ammonium iodide salt in a role similar to that of Lil [8]. Beneficial effects on rhodium-complex-catalyzed methanol carbonylation have also been found for other additives. For example, phosphine oxides such as Ph3PO enable high catalyst rates at low water concentrations without compromising catalyst stability [40—42]. Similarly, iodocarbonyl complexes of ruthenium and osmium (as used to promote iridium systems, Section 3) are found to enhance the activity of a rhodium catalyst at low water concentrations [43,44]. Other compounds reported to have beneficial effects include phosphate salts [45], transition metal halide salts [46], and oxoacids and heteropolyacids and their salts [47]. [Pg.10]


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See also in sourсe #XX -- [ Pg.97 ]




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Carbonyl effect

Carbonylation catalyzed

Carbonylation, iridium-catalyzed

Catalyzed Carbonylations

Iridium carbonylation

Iridium carbonyls

Iridium-catalyzed carbonylations

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