Monoepoxides rearrangement

The synthesis of vinyl epoxides from dienes is mentioned in Chapter 19. The monoepoxide is formed first as the diene is more nucleophilic than the alkene in the monoepoxide. The main difficulty is that the monoepoxide rearranges with acid catalysis from the by-product, the carboxylic acid of the peroxyacid used in the epoxidation. The solution is simple the mixture must be buffered to keep the acidity low. 

Rearrangements are also observed during halojluonnanons with cyclic medium ring dienes [70, 93] (equations 4 and 5) and with the monoepoxide of 1,5-cyclooctadiene [94] (equation 6) during halofluonnations Again, there are differences in product mixture with apparently minor variations in reagents (equation 4)... 

Epoxidation of norbornene was found some time prior to this work not to stop at the monoepoxide step. Instead, this intermediate goes on to rearrange to the bicyclic aldehyde, 31, ... 

As described in the preceding paragraphs, oxidation products of carotenoids can be formed in vitro as a result of their antioxidant or prooxidant actions or after their autoxidation by molecular oxygen. They can also be found in nature, possibly as metabolites of carotenoids. Frequently encountered products are the monoepoxide in 5,6- or 5, 6 -positions and the diepoxide in 5,6 5, 6 positions or rearrangement products creating furanoid cycles in the 5,8 or 5, 8 positions and 5,8 5, 8 positions, respectively. Products like apo-carotenals and apo-carotenones issued from oxidative cleavages are also common oxidation products of carotenoids also found in nature. When the fission occurs on a cyclic bond, the C-40 carbon skeleton is retained and the products are called seco-carotenoids. 

Sharer, J.E., Duescher, R.J. Elfarra, A. A. (1991) Formation, stability and rearrangements of the glutathione conjugates of butadiene monoepoxide evidence for the formation of stable sulfu-rane intermediates. Chem. Res. Toxicol., 4, 430 36... 

The third type is common to monoepoxides of cyclic 1,3-dienes In five- to eight-membered rings and results in rearrangement to /3,y-unsaturated ketones in 55-80% yield. This isomerization can be utilized as one step in a route to 4-hydroxy-2-cycloenones. An example is a synthesis of 4-hydroxy-2-cyclopentenone formulated in equation (III). 

Levopimaric acid forms an epidioxide (63) which thermally rearranges to a di oxide (65). On photolysis the epidioxide gives both the diepoxide and the 12-keto-epoxide (64). Treatment of the epidioxide with triphenylphosphine affords a monoepoxide which was shown to be the 8a(14a)-epoxide (66). On further epoxidation this gave the diepoxide, levopimaric acid dioxide. The photochemistry of ring c diterpenoid y-hydroxydienones has also been investi-gated. " Thus compound (67 R = H or Et) afforded firstly the spiro-diketone (68) and then the unsaturated y-lactone (69). 

Transannular hydride shifts, first detected by Cope and coworkers in solvolyses of cyclooctene oxide, have subsequently been found in a number of related systems, e.g. cyclooctadiene monoepoxides, CA o-bicyclo[3.3.1 ]non-2-ene epoxide and l-oxaspiro[2.6]nonane. In general these reactions do not involve skeletal rearrangements, and they will not be discussed in detail. 

Matsuda and Sugishita found that cyclooctatetraene monoepoxide (233 equation 99) gave only skeletally rearranged products, e.g. (234), when treated with Grignard reagents. In an effort to isolate the presumed intermediate cycloheptatrienecarbaldehyde, (233) was subjected to a catalytic amount of MgBra, but this resulted in the formation of phenylacetaldehyde. 

An organoaluminum compound in hydrocarbon solvent caused rearrangement of an acid-sensitive diene monoepoxide, but a change to ether solvent mediated this (undesired) reaction. 

The Simmons-Smith cyclopropanation reaction Stereochemically controlled epoxidations Regio- and Stereocontrolled Reactions with Nucleophiles Claisen-Cope rearrangements Stereochemistry in the Claisen-Cope rearrangement The Claisen-Ireland rearrangement Pd-catalysed reactions of allylic alcohols Pd-allyl acetate complexes Stereochemistry of Pd-allyl cation complexes Pd and monoepoxides of dienes The control of remote chirality Recent developments Summary... 

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