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Subject carbonyls

Finally, if there could be a way in which in water selective ri Jt-coordination to the carbonyl group of an a,P-imsatLirated ketone can be achieved, this would be a breakthrough, since it would subject monodentate reactants to catalysis by hard Lewis acids ". ... [Pg.169]

In an extension of the work described m the preceding section Bender showed that basic ester hydrolysis was not concerted and like acid hydrolysis took place by way of a tetrahedral intermediate The nature of the experiment was the same and the results were similar to those observed m the acid catalyzed reaction Ethyl benzoate enriched m 0 at the carbonyl oxygen was subjected to hydrolysis m base and samples were isolated before saponification was complete The recovered ethyl benzoate was found to have lost a por tion of Its isotopic label consistent with the formation of a tetrahedral intermediate... [Pg.855]

The subject has been reviewed (37,38). Water may be added to the feed to suppress methyl acetate formation, but is probably not when operating on an industrial scale. Water increase methanol conversion, but it is involved in the unavoidable loss of carbon monoxide. A typical methanol carbonylation flow sheet is given in Figure 2. [Pg.68]

There are at least two mechanisms available for aziridine cis-trans isomerism. The first is base-catalyzed and proceeds via an intermediate carbanion (235). The second mechanism can be either thermally or photochemically initiated and proceeds by way of an intermediate azomethine ylide. The absence of a catalytic effect and interception of the 1,3-dipole intermediate provide support for this route. A variety of aziridinyl ketones have been found to undergo equilibration when subjected to base-catalyzed conditions (65JA1050). In most of these cases the cis isomer is more stable than the trans. Base-catalyzed isotope exchange has also been observed in at least one molecule which lacks a stabilizing carbonyl group (72TL3591). [Pg.72]

The mechanism by which this low oxidation state is stabilized for this triad has been the subject of some debate. That it is not straightforward is clear from the fact that, in contrast to nickel, palladium and platinum require the presence of phosphines for the formation of stable carbonyls. For most transition metals the TT-acceptor properties of the ligand are thought to be of considerable importance and there is... [Pg.1166]

Chiral salen chromium and cobalt complexes have been shown by Jacobsen et al. to catalyze an enantioselective cycloaddition reaction of carbonyl compounds with dienes [22]. The cycloaddition reaction of different aldehydes 1 containing aromatic, aliphatic, and conjugated substituents with Danishefsky s diene 2a catalyzed by the chiral salen-chromium(III) complexes 14a,b proceeds in up to 98% yield and with moderate to high ee (Scheme 4.14). It was found that the presence of oven-dried powdered 4 A molecular sieves led to increased yield and enantioselectivity. The lowest ee (62% ee, catalyst 14b) was obtained for hexanal and the highest (93% ee, catalyst 14a) was obtained for cyclohexyl aldehyde. The mechanism of the cycloaddition reaction was investigated in terms of a traditional cycloaddition, or formation of the cycloaddition product via a Mukaiyama aldol-reaction path. In the presence of the chiral salen-chromium(III) catalyst system NMR spectroscopy of the crude reaction mixture of the reaction of benzaldehyde with Danishefsky s diene revealed the exclusive presence of the cycloaddition-pathway product. The Mukaiyama aldol condensation product was prepared independently and subjected to the conditions of the chiral salen-chromium(III)-catalyzed reactions. No detectable cycloaddition product could be observed. These results point towards a [2-i-4]-cydoaddition mechanism. [Pg.162]

Pure piperitone was subjected to the action of purified hydrogen, in the presence of a nickel catalyst, for six hours, the temperature ranging between 175° to 180° C. The double bond in piperitone was readily opened out with the formation of menthone, but further action of the hydrogen under these conditions did not reduce the carbonyl group, even after continued treatment for two days. Under correct conditions, however, the reduction to menthol should take place. The ease with which menthone is formed in this way is of special interest, not only in connection with the production of this ketone, but also as a stage in the manufacture of menthol. [Pg.240]

Modular Presentation Topics are arranged in a roughly modular way. Thus, certain chapters are grouped together simple hydrocarbons (Chapters 3-8), spectroscopy (Chapters 12-14), carbonyl-group chemistry (Chapters 19-23), and biomolecules (Chapters 25-29). 1 believe that this organization brings to these subjects a cohesiveness not found in other texts and allows the instructor the flexibility to teach in an order different from that presented in the book. [Pg.1336]

The homology between 22 and 21 is obviously very close. After lithium aluminum hydride reduction of the ethoxycarbonyl function in 22, oxidation of the resultant primary alcohol with PCC furnishes aldehyde 34. Subjection of 34 to sequential carbonyl addition, oxidation, and deprotection reactions then provides ketone 21 (31% overall yield from (—)-33). By virtue of its symmetry, the dextrorotatory monobenzyl ether, (/ )-(+)-33, can also be converted to compound 21, with the same absolute configuration as that derived from (S)-(-)-33, by using a synthetic route that differs only slightly from the one already described. [Pg.199]

You will note that the oxygen atoms attached to carbons 5 and 12 in 43 reside in proximity to the C-9 ketone carbonyl. Under sufficiently acidic conditions, it is conceivable that removal of the triethylsilyl protecting groups would be attended by a thermodynamically controlled spiroketalization reaction.30 Indeed, after hydro-genolysis of the C-26 benzyl ether in 43, subjection of the organic residue to the action of para-toluenesulfonic acid in a mixture of methylene chloride, ether, and water accomplishes the desired processes outlined above and provides monensin methyl ester. Finally, saponification of the methyl ester with aqueous sodium hydroxide in methanol furnishes the sodium salt of (+)-monensin [(+)-1], Still s elegant synthesis of monensin is now complete.13... [Pg.246]

Subjection of intermediate 16 to the action of 3 n aqueous HC1 in THF results in the formation of monocyclic lactol 14. In the presence of aqueous acid, the internal acetal grouping in intermediate 16 is hydrolyzed and lactol 14 is produced after the liberated secondary hydroxyl group attacks the terminal aldehyde carbonyl positioned five atoms away (see intermediate 15). Protection of the free aldehyde function in 14 with 1,1-dimethylhydrazine proceeds smoothly under dehydrating conditions and affords intermediate 13 in an overall yield of 72 %. [Pg.326]

This area of reactivity has been the subject of excellent reviews (J5). Silyl enol ethers are not sufficiently nucleophilic to react spontaneously with carbonyl compounds they do so under the influence of either Lewis acids or fluoride ion, as detailed above. Few clear trends have emerged from the somewhat limited number of definitive studies reported so far, with ambiguities in diastereoisomeric assignments occasionally complicating the issue even further. [Pg.68]


See other pages where Subject carbonyls is mentioned: [Pg.56]    [Pg.168]    [Pg.852]    [Pg.78]    [Pg.69]    [Pg.391]    [Pg.496]    [Pg.153]    [Pg.86]    [Pg.412]    [Pg.11]    [Pg.643]    [Pg.169]    [Pg.45]    [Pg.116]    [Pg.20]    [Pg.318]    [Pg.105]    [Pg.149]    [Pg.1335]    [Pg.142]    [Pg.144]    [Pg.171]    [Pg.233]    [Pg.607]    [Pg.649]    [Pg.760]    [Pg.764]    [Pg.781]    [Pg.300]    [Pg.11]    [Pg.174]    [Pg.175]    [Pg.282]    [Pg.140]    [Pg.57]    [Pg.80]    [Pg.34]    [Pg.135]   
See also in sourсe #XX -- [ Pg.367 ]

See also in sourсe #XX -- [ Pg.2 , Pg.5 , Pg.8 , Pg.9 , Pg.63 ]




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Carbonyl complexes, chromium 364 Subject

Carbonyl compounds Subject

Carbonyl reduction 486 Subject

Cumulative Subject carbonyl compounds

Cumulative Subject reaction with carbonyl compounds

Cumulative Subject unsaturated carbonyl compounds

Iron carbonyl Subject

Metal carbonyls 454 Subject

Subject addition to carbonyl compounds

Subject carbonyl complexes

Subject carbonyl displacement

Subject carbonyl group protection

Subject carbonyl group regeneration

Subject carbonyl methylenation

Subject carbonyl sulfide

Subject carbonyl ylide generation

Subject carbonylation

Subject carbonylation

Subject carbonylation reactions

Subject carbonyls with alkenes

Subject reactions with carbonyl compounds

Subject reductive carbonylation

Subject transition metal carbonyl complexes

Subject unsaturated carbonyl compounds

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