1,5-cyclooctadiene hydrogenation

Figure 4.1.13 COD conversion (A) and COE selectivity (B) at different hydrogen pressures, 50°C, and ccoD.cr 0.41 mol/L. Simulation (lines) and experimental data (symbols). Unchanged figure adapted from [16], Reprinted from Industrial Engineering Chemistry Research, Yol. 46, A. Schmidt and R. Schomacker, Kinetics of 1,5-cyclooctadiene hydrogenation on Pd/a-AI2O3,103-110, Copyright (2007), with permission from Elsevier via the Copyright Clearance Center.

Although the hydrogenation rate of 1,5-cyclooctadiene is lower in ethanol and 1-propanol than in methanol, the selectivity is the same [43]. The PVPD-Pd catalyst is insoluble in ethyl acetate and tetrahydrofuran and shows low activity. The rate of 1,3- and 1,5-cyclooctadiene hydrogenation is expressed by the following equation ... 

Is cyclooctatetraene aromatic To tell, compare the first and second hydrogenation energies, leading to 1,3,5-cyclooctatriene and then to 1,3-cyclooctadiene. (The energy for hydrogen is provided at left.)... 

Figure3.60 Gas-phase hydrogenation ofl, 5-cyclooctadiene. Conversion and selectivitydependingon hydrogen partial pressure[l 30],...

Based upon the above-mentioned assumptions, the reaction scheme in Figure 3.1 is reduced to the scheme shown in Figure 3.2A. It should be noted that active catalyst is used in the reaction scheme in Figure 3.1 while most asymmetric hydrogenation processes use a pre-catalyst (11). Hence, the relationship between the precatalyst and active catalyst needs to be established for the kinetic model. The precatalyst used in this study is [Et-Rh(DuPhos)(COD)]BF4 where COD is cyclooctadiene. The active catalyst (Xq) in Figure 3.2A is formed by removal of COD via hydrogenation, which is irreversible. We assume that the precatalyst is completely converted to the active catalyst Xq before the start of catalytic reaction. Hence, the kinetic model derived here does not include the formation of the active catalyst from precatalyst. 

Manufacture of rhodium precatalysts for asymmetric hydrogenation. Established literature methods used to make the Rh-DuPhos complexes consisted of converting (1,5-cyclooctadiene) acetylacetonato Rh(l) into the sparingly soluble bis(l,5-cyclooctadiene) Rh(l) tetrafluoroborate complex which then reacts with the diphosphine ligand to provide the precatalyst complex in solution. Addition of an anti-solvent results in precipitation of the desired product. Although this method worked well with a variety of diphosphines, yields were modest and more importantly the product form was variable. The different physical forms performed equally as well in hydrogenation reactions but had different shelf-life and air stability. 

The stereochemistry of reduction by homogeneous catalysts is often controlled by functional groups in the reactant. Delivery of hydrogen occurs cis to a polar functional group. This behavior has been found to be particularly characteristic of an iridium-based catalyst that contains cyclooctadiene, pyridine, and tricyclohexylphosphine as ligands, known as the Crabtree catalyst 6 Homogeneous iridium catalysts have been found to be influenced not only by hydroxy groups, but also by amide, ester, and ether substituents.17... 

Presumably, the stereoselectivity in these cases is the result of coordination of iridium by the functional group. The crucial property required for a catalyst to be stereodirective is that it be able to coordinate with both the directive group and the double bond and still accommodate the metal hydride bonds necessary for hydrogenation. In the iridium catalyst illustrated above, the cyclooctadiene ligand (COD) in the catalysts is released by hydrogenation, permitting coordination of the reactant and reaction with hydrogen. 

These catalysts are activated by hydrogenation of the cyclooctadiene ligand, which releases cyclooctane and opens two coordination sites at iridium. The mechanism has been probed by computational studies.40 It is suggested that the catalytic cycle involves... 

In many cases the transformations may be more complex than indicated by Eqs. (9.89)-(9.100). An example of this is the photochemistry of cis,cis-1,3-cyclooctadiene [Eq. (9.94)].<169) A close examination of this reaction indicates that bicyclo[4.2.0]oct-7-ene is formed but in low relative yields during the initial reaction (see Table 9.9). In addition, the cis,trans-1,3-cyclooctadiene is formed and then consumed as the reaction proceeds. Fonken showed that the bicyclooctene initially formed, however, was not from thermal isomerization of the cis,trans-diene. Still a third reaction was the 1,3 sigmatropic hydrogen shift to form the cis, cis-1,4-cyclooctadiene ... 

By contrast, much of the work performed using ruthenium-based catalysts has employed well-defined complexes. These have mostly been studied in the ATRP of MMA, and include complexes (158)-(165).400-405 Recent studies with (158) have shown the importance of amine additives which afford faster, more controlled polymerization.406 A fast polymerization has also been reported with a dimethylaminoindenyl analog of (161).407 The Grubbs-type metathesis initiator (165) polymerizes MMA without the need for an organic initiator, and may therefore be used to prepare block copolymers of MMA and 1,5-cyclooctadiene.405 Hydrogenation of this product yields PE-b-PMMA. N-heterocyclic carbene analogs of (164) have also been used to catalyze the free radical polymerization of both MMA and styrene.408... 

---