Formamides catalysts

A selection of the most efficient formamide catalysts based on amino acids is shown in Figures 4.1 and 4.2 representative examples of enantioselective hydro silylation are listed in Tables 4.1 4.7. The proline derived anilide 16 and its naphthyl analogue 17, introduced by Matsumura as the first chiral catalysts [10], exhibited moderate enantioselectivity in the reduction of aromatic ketimines with trichloro silane at 10mol% catalyst loading (Table 4.1, entries 1 and 2). The formamide... 

AZDN[Azo-Di(Carbonamide)] orABFA [Azo-bis(Formamide)]. Catalysts permit use at lower temperatures coarse particle size permits use at higher temperatures. It is widely used in commodity thermoplastics and even some engineering thermoplastics about 90 percent of the market. 

Scheme 31 Model L-pipecolinic acid derived A -formamide catalysts 86-88...

Figure 15.1 Examples of chiral Lewis-basic phosphoramide and formamide catalysts. The ee refers to the reaction of benzaldehyde with 2a.

The concept of connecting two L-prolinamides portions over a chiral backbone structure was applied on the C2-symmetrical bis-formamide catalyst 68 for the... 

The carbonylation of methanol [67-56-1] to methyl formate ia the presence of basic catalysts has been practiced iadustriaHy for many years. Ia older processes for formic acid utili2ing this reactioa, the methyl formate [107-31-3] reacts with ammonia to give formamide [75-12-7] which is hydroly2ed to formic acid ia the preseace of sulfuric acid ... 

Formamide decomposes thermally either to ammonia and carbon monoxide or to hydrocyanic acid and water. Temperatures around 100°C are critical for formamide, in order to maintain the quaUty requited. The lowest temperature range at which appreciable decomposition occurs is 180—190°C. Boiling formamide decomposes at atmospheric pressure at a rate of about 0.5%/min. In the absence of catalysts the reaction forming NH and CO predominates, whereas hydrocyanic acid formation is favored in the presence of suitable catalysts, eg, aluminum oxides, with yields in excess of 90% at temperatures between 400 and 600°C. 

Early in the twentieth century, the first attempts to manufacture formamide directiy from ammonia and carbon monoxide under high temperature and pressure encountered difficult technical problems and low yields (23). Only the introduction of alkaU alkoxides in alcohoHc solution, ie, the presence of alcoholate as a catalyst, led to the development of satisfactory large-scale formamide processes (24). 

In addition to the processes mentioned above, there are also ongoing efforts to synthesize formamide direcdy from carbon dioxide [124-38-9J, hydrogen [1333-74-0] and ammonia [7664-41-7] (29—32). Catalysts that have been proposed are Group VIII transition-metal coordination compounds. Under moderate reaction conditions, ie, 100—180°C, 1—10 MPa (10—100 bar), turnovers of up to 1000 mole formamide per mole catalyst have been achieved. However, since expensive noble metal catalysts are needed, further work is required prior to the technical realization of an industrial process for formamide synthesis based on carbon dioxide. 

Formamide has been alkylated with methanol ia the presence of a metal catalyst to give DMF (22). The alkylation reaction can also be catalyzed by tetralkylammonium salts (23). 

The Jacobsen group has also shown that the recycling of the resin-bounded catalyst can be successfully performed [152,154]. Moreover, they have developed an efficient method for the hydrolysis of the aminonitrile into the corresponding amino acid. This method was apphed for the commercial production of optically active K-amino acids at Rhodia ChiRex (e.g. tert-leucine) the catalyst was immobihsed on a resin support (4 mol %, 10 cycles) and the intermediate hydrocyanation adduct was trapped by simply replacing TFAA with HCOOH/AC2O, for example. Highly crystalhne formamide derivatives were thus obtained in excellent yields (97-98% per cycle) with very high enantioselectivities (92-93% per cycle) [158]. 

Several reactions have been demonstrated using microreactors. One of the potentially more important is the direct synthesis of MIC from oxygen and methyl formamide over a silver catalyst. Dupont have demonstrated this process using a microreactor cell similar to that described above in which the two reactants are mixed, then heated to 300 °C in a separate layer and subsequently passed through another tube coated with the silver catalyst. The estimated capacity of a single cell with tube diameters of a few millimetres is 18 tpa. 

Gold(I) complexes of the type [AuCl(PPh3)ra] (n= 1, 2) or [Au(N03)(PPh3)] show an excellent performance towards oxidative addition carbonylation or aromatic amines to form corresponding carbamates, and also towards the carbonilation of aliphatic amines to produce either alkylureas or formamides.2552,2553 Cationic gold(I) compounds of the type [AuL]+ where L = phosphine, phosphite, or arsine are excellent catalysts for the addition of alcohols to alkynes.2554... 

Highly efficient catalysts have been developed for the hydrogenation of C02 to formic acid and formamides, to the point where industrialization could be considered. Researchers have been far less successful in developing efficient homogeneous catalysts and optimum conditions for the hydrogenation of C02 to alkyl formates, methanol, methane, and especially oxalic acid. These are the areas in which research efforts are most needed. 

Although understanding the effect of the a-substituent on relative alkyl hydride stabilities is straightforward, understanding the effect on the catalyst-enamide diastereomers is not. To clarify this matter we performed a series of calculations on a variety of substituted enamides [78], To eliminate the effect of the amide oxygen, we examined frontier orbitals of the [Rh(PH3)2(formamide)]+ fragment (15) and those of model enamides (16). 

CO oxidation, 38 236 differential heat of adsorption, 38 217 Biphasic systems, catalysis see Multiphase homogeneous catalysis BiPMo catalysts, 34 39 in formamide to nitrile reaction, 34 39 Bi-postdosing thermal desorption spectroscopy cyclohexene, 42 240... 

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