Hydrogenation condition

Rigorous hydrogenating conditions, particularly with Raney Nickel, remove the sulfur atom of thiophenes. With vapor-phase catalysis, hydrodesulfurization is the technique used to remove sulfur materials from cmde oil. Chemically hydrodesulfurization can be a valuable route to alkanes otherwise difficult to access. 

Some advantages of the Fmoc protective group are that it has excellent acid stability thus BOC and benzyl-based groups can be removed in its presence. It is readily cleaved, nonhydrolytically, by simple amines, and the protected amine is liberated as its free base. The Fmoc group is generally considered to be stable to hydrogenation conditions, but it has been shown that under some circumstances it can be cleaved with H2/Pd-C, AcOH, MeOH, (t /2 = 3-33 h). ... 

Normally, the hydrogenation of a readily hydrogenated double bond occurs over palladium-on-charcoal in ethanol at room temperature and atmospheric pressure. The more difficultly reduced olefins require elevated reaction temperatures and/or pressures for the reaction to proceed at a reasonable rate. The saturation of an 8(14)-double bond is virtually impossible under normal hydrogenation conditions. In order to remove unsaturation at this position it is necessary to first isomerize the double bond to the readily hydrogenated 14 position by treatment with dry hydrogen chloride in chloro-form. ° ... 

Other PK variations include microwave conditions, solid-phase synthesis, and the fixation of atmospheric nitrogen as the nitrogen source (27—>28). Hexamethyldisilazane (HMDS) is also an excellent ammonia equivalent in the PK synthesis. For example, 2,5-hexanedione and HMDS on alumina gives 2,5-dimethylpyrrole in 81% yield at room temperature. Ammonium formate can be used as a nitrogen source in the PK synthesis of pyrroles from l,4-diaryl-2-butene-l,4-diones under Pd-catalyzed transfer hydrogenation conditions. 

It was assumed that pyridine derivative 181 yielded pyrido[l,2-c]pyrimidine betaine 182 under catalytic hydrogenation conditions over (5,S)-Et-DuPHoS-Ph catalyst (99TL1211). 6,7-Dehydro derivative 184 of trequinsin (3) was obtained from pyrimidinone 183 by heating in an 1 1 mixture of MeOH and cone. HCl under reflux (97IJC(B)349). 

Double-bond migration often passes unnoticed, for unless tracers are employed, there may be no direct evidence remaining that migration has occurred. Nonetheless, the fact that it does occur can have a number of important consequences. Selective removal of cis homoconjugated dienes and trienes in natural oils, used to make edible hydrogenated fats, depends mainly on prior isomerization of multiple unsaturation into conjugation under hydrogenation conditions (J9). 

Homoallylic systems may isomerize under hydrogenation conditions to allylic systems, causing hydrogenolysis to occur when it would not have been expected (39b,45a-45c). In these cases, if hydrogenolysis is unwanted, it is best to avoid those catalysts and conditions that favor isomerization. Double-bond migration to an allylic position may occur even if the double bond is required to leave a tetrasubstituted position (26a). 

The catalytic hydrosi(ly)lations of other C=X functional groups (X = O, NR) constitute alternative routes to the reduction of aldehydes, ketones, imines and other carbonyl compounds (Scheme 2.9), circumventing the use of molecular hydrogen or occasionally harsh transfer hydrogenation conditions. 

The asymmetric reduction of enamides using hydrogenation conditions is a well documented reaction with a number of groups reporting excellent results [14]. Syn delivery of hydrogen from the same face of the molecule ensures that the enamide geometry defines the relative stereochemistry obtained, and a range of chiral catalysts have been developed to control the absolute stereochemistry. However, a... 

With all other pieces of the synthesis in place our attention now focused on the final piece in the jigsaw-the asymmetric hydrogenation of the amide enamide 42. Screening of hydrogenation conditions rapidly led to identification of a number of conditions which allowed the desired hydrogenation to proceed at low catalyst loadings and in non-chlorinated solvents (Table 9.9). 

The catalytic system employing (2 - Fur)3P as ligand was applied to the coupling of methyl vinyl ketone and ethyl vinyl ketone to aromatic, aliphatic, acetylenic, and olefinic aldehydes (Scheme 23) [37]. Despite the hydrogenation conditions, alkyne and alkene moieties, as well as benzylic ether and nitro functional groups all remained intact. Furthermore, extremely high lev-... 

Scheme 24) [38]. Chemoselective enolization of the less substituted enone moiety under hydrogenation conditions accompanied by subsequent aldol reaction provided the corresponding hydroxyl-enones, such as 87-89, which could be converted to various building blocks for polypropionate synthesis. p-Me2N styryl vinyl enone also was employed successfully as an enolate precursor, as demonstrated by the formation of hydroxy enone 90. 

Figure 5 Conversion and Product Selectivity for Ni/Re Catalyst over 1700 hours, aqueous hydrogenation condition (unspecified).

If we compare these productivities with those obtained under catalytic hydrogenation conditions (Table 2, Figure 3), we can see that the trend is different Cu/MgO shows very low activity, particularly if compared with that of the catalyst supported on silica and modified silicas. 

Geraniol can be converted into citronellol and menthol over Cu/A1203 under catalytic hydrogenation conditions owing to chemoselective hydrogenation and a three-functional process taking place on the catalyst surface. 

Here we report that geraniol 1, under catalytic hydrogenation conditions in the presence of a Cu/A1203 catalyst, gives two valuable products, namely citronellol 2 and menthol 3. 

The oxazolidine ring proved to be stable toward hydrogenation conditions using 10% Pd/C and (Boc)20 in CH2Cl2 (Scheme 4.153).592... 

Competitive reduction tests for cyclohexanone styrene, under transfer conditions, show preferential reduction of cyclohexanone however, under hydrogenation conditions the styrene is reduced exclusively.99 It is worth mentioning that the OsH2(r)2-H2)(CO)(P Pr3)2 precatalyst, formed by addition of NaBH4 to OsHCl (CO)(P Pr3)2, rapidly reduces phenylacetylene to styrene, under transfer conditions, but the reaction rate falls progressively due to the formation of Os(C=CPh)2 (CO)(P Pr3)2.72 As previously mentioned, an alkynyl-dihydrogen intermediate... 

Experimental data published recently by Cudmore (10) for eight Australian bituminous coals, reproduced in Fig. 2, show a direct linear correlation between conversion (to gas + liquids), under non-catalytic hydrogenation conditions using Tetralin as... 

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