Osmium hydrogenation, selective

The next step involved the selective reduction of one of the double bonds in 12, specifically the double bond in ring C. No reliable method existed to secure the required hydrogenation selectivity. Therefore, the double bond in ring D was hydroxylated with osmium tetroxide and the resulting diol converted into the corresponding acetal 13. In addition to simplifying the selectivity problem... 

A Belgian patent (178) claims improved ethanol selectivity of over 62%, starting with methanol and synthesis gas and using a cobalt catalyst with a hahde promoter and a tertiary phosphine. At 195°C, and initial carbon monoxide pressure of 7.1 MPa (70 atm) and hydrogen pressure of 7.1 MPa, methanol conversions of 30% were indicated, but the selectivity for acetic acid and methyl acetate, usehil by-products from this reaction, was only 7%. Ruthenium and osmium catalysts (179,180) have also been employed for this reaction. The addition of a bicycHc trialkyl phosphine is claimed to increase methanol conversion from 24% to 89% (181). 

Osmium makes a sluggish carbonyl hydrogenation catalyst but has the unusual property of reducing a, -unsaturated aldehydes to the unsaturated alcohol in good yield (85). The system has proved erratic high selectivity can only be obtained through prereduction of the catalyst just before use. 

Reduction of unsaturated aldehydes seems more influenced by the catalyst than is that of unsaturated ketones, probably because of the less hindered nature of the aldehydic function. A variety of special catalysts, such as unsupported (96), or supported (SJ) platinum-iron-zinc, plalinum-nickel-iron (47), platinum-cobalt (90), nickel-cobalt-iron (42-44), osmium (<55), rhenium heptoxide (74), or iridium-on-carbon (49), have been developed for selective hydrogenation of the carbonyl group in unsaturated aldehydes. None of these catalysts appears to reduce an a,/3-unsaturated ketonic carbonyl selectively. 

Independent studies of the reduction of C=C and C=C bonds indicate that the latter is kinetically favored. Thus, in the absence of phenylacetylene, the rate of hydrogenation of styrene to ethylbenzene is about one order of magnitude faster than those for C=C bond reduction, indicating that the origin of the selectivity cannot be kinetic. The styryl compound represents a thermodynamic sink that causes virtually all the osmium present in solution to be tied up in this form, and therefore the kinetically unfavorable pathway becomes essentially the only one available in the presence of alkyne.31... 

In such reactions, a temperature exceeding 130°C has a dramatic effect on the catalytic activity. The pressure of hydrogen has a similar effect, with a large increase in activity above 30 bar. These catalysts did not exhibit the same selectivity for ketones. Osmium triphenylphosphine systems have been briefly exam-... 

Unsaturated aliphatic aldehydes were selectively reduced to unsaturated alcohols by specially controlled catalytic hydrogenation. Citral treated with hydrogen over platinum dioxide in the presence of ferrous chloride or sulfate and zinc acetate at room temperature and 3.5 atm was reduced only at the carbonyl group and gave geraniol (3,7-dimethyl-2,6-octadienol) [59], and crotonaldehyde on hydrogenation over 5% osmium on charcoal gave crotyl alcohol [763]. 

A 95% yield of cinnamic alcohol is obtained by selective hydrogenation of the carbonyl group in cinnamaldehyde with, for example, an osmium-carbon catalyst [145]. 

Osmium complexes modified with tppts and tppms also catalyse the selective hydrogenation of cinnamaldehyde to cinnamylalcohol (Figure 14, II) in an aqueous/organic two phase system.493 The selectivity towards the unsaturated alcohol II with Os/tppts was lower than with Ru/tppts but both Ru and Os/tppts... 

Miscellaneous. Aside from the oxidation chemistry described, only a few catalytic applications are reported, including hydrogenation of olefins (114,115), a, [3-unsaturated carbonyl compounds (116), and carbon monoxide (117) and the water gas shift reaction (118). This is so owing to the kinetic inertness of osmium complexes. A 1% by weight osmium tetroxide solution is used as a biological stain, particulady for preparation of samples for electron microscopy. In the presence of pyridine or other heterocyclic amines it is used as a selective reagent for single-stranded or open-form B-DNA (119) (see Nucleic acids). Osmium tetroxide has also been used as an indicator for unsaturated fats in animal tissue. Osmium tetroxide has seen limited if controversial use in the treatment of arthritis (120,121). 

Contrast in the TEM increases as the atomic number of the atoms in the specimen increases. Since biological molecules are composed of atoms of very low atomic number (carbon, hydrogen, nitrogen, and so on), contrast is increased with a selective staining, obtained by exposure of the specimen to salts of heavy metals, such as uranium, lead, and osmium, which are electron opaque (www.hei.org/research/depts/aemi/emt.htm). 

An alternate entry to the narciclasine class of alkaloids has provided access to compounds related to isonarciclasine (263) (Scheme 24). In the event, the aryla-tion of p-benzoquinone with diazonium salts derived from the aryl amines 250 and 251 yielded the aryl-substituted benzoquinones 252 and 253, respectively (146). The selective hydroxylation of 252 and 253 with osmium tetraoxide provided the corresponding m-diols 254 and 255. Catalytic hydrogenation of 254 and 255 using Pd/C or Raney Ni and subsequent lactonization gave the triols 256 and 257 together with small amounts of the C-2 a-epimers 258 and 259. Aminolysis of 256 and 257 afforded the corresponding racemic tetrahydrophen-anthridones 260 and 261, whereas similar treatment of the a-epimers 258 and 259 led to the formation of ( )-isolycoricidine (262) and ( )-isonarciclasine (263), respectively. 

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