Amine 1-hexene, effect

Table 3 summarizes the scope and limitation of substrates for this hydrogenation. Complex 5 acts as a highly effective catalyst for functionalized olefins with unprotected amines (the order of activity tertiary > secondary primary), ethers, esters, fluorinated aryl groups, and others [27, 30]. However, in contrast to the reduction of a,p-unsaturated esters decomposition of 5 was observed when a,p-unsaturated ketones (e.g., trans-chalcone, trans-4-hexen-3-one, tra s-4-phenyl-3-buten-2-one, 2-cyclohexanone, carvone) were used (Fig. 3) [30],... 

The stability of olefin complexes is also sensitive to steric effects. The binding of ethylene is stronger than that of a-olefins in nearly all cases. However, the magnitude of the steric effect on the binding of an olefin depends on the other ligands. For example, the ethylene complex of bis(amine)PdMe in Equation 2.11b is 10-fold more stable than the propylene or hexene complex, while flie ethylene complex of PtClj" is ortiy two-fold more stable than the corresponding propene complex. ... 

Even simple alkenes, such as 1-hexene 9.270, can yield ir-allyl complexes on reaction with vinyl halides under Heck conditions (Scheme 9.75). This is only apparent when a nucleophile is present, such as a secondary amine or a malonate anion. The ir-allyl complex 9.279 is generated by isomerization of the corresponding T -complex 9.278 that is itself generated by a -hydride elimination-reinsertion sequence from the initial insertion product 9.275. Nucleophilic attack on the Tr-allyl complex gives the three component coupling product 9.273, while the Heck product, diene 9.272, can arise from dissociation from t -complex 9.276 or p-hydride elimination from the -intermediate 9.278. Again, the reaction is particularly effective in an intramolecular sense. °°... 

When Co2Rh2(CO)j 2 mixture of Co4(CO)i2 and Rh4(CO)j2 was impregnated onto organic Dowex resins, active hydroformylation catalysts came out [98]. With amine groups in the resin or the addition of NEtj in the hydroformylation of 1-hexene, the corresponding nonanols were formed exclusively with a yield of 95%. The ratio of Rh/Co had a marked effect on the product distribution. Best results were observed with Rh/Co ratios of 2.6-3.6. Other functional groups in the resin did not force the formation of alcohols. 

An interesting comparison of catalytic activities of synthetic beidellite and montmorillonite and PILCS prepared from them was recently reported [69]. The reactions examined included secondary amine formation from cyclohexylamine, ester production from 1-hexene and acetic acid and ether synthesis from pentanol. In all cases, the reactivity of the PILCS was much lower than that of the unpillared clays, whereas the montmorillonite was generally more effective than the beidellite. These results are not surprising in that all of the reactions are Br<(Jnsted-acid-catalyzed and the observed decreased activity of the PILCS may derive from a greater loss of protons to the layers by the pillared clays. This is also in keeping with the findings of Occelli and Tindwa [5] that the PILCS are mainly Lewis acids after heat treatment. 

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