Direct disparlure

It should be added that many other groups have contributed to the predevelopments of these inventions and also to later developments. All four reactions find wide application in organic synthesis. The Sharpless epoxidation of allylic alcohols finds industrial application in Arco s synthesis of glycidol, the epoxidation product of allyl alcohol, and Upjohn s synthesis of disparlure (Figure 14.4), a sex pheromone for the gypsy moth. The synthesis of disparlure starts with a Ci3 allylic alcohol in which, after asymmetric epoxidation, the alcohol is replaced by the other carbon chain. Perhaps today the Jacobsen method can be used directly on a suitable Ci9 alkene, although the steric differences between both ends of the molecules are extremely small ... 

Its longest continuous chain contains 18 carbon atoms, and so it is named as an epoxy derivative of octadecane. Number the chain in the direction that gives the lowest number to the carbons that bear oxygen. Thus, disparlure is d.v-2-mcthyl-7,8-cpoxyoctadccanc. 

Directing effects of substituents. See Electrophilic aromatic substitution Disaccharide, 973, 991-993, 1008. See also Cellobiose Lactose Maltose Sucrose Disparlure, 239... 

This methodology [94TL3601] was used to construct the optically active erythro-diol 8, which was then stereospecifically converted to (+)- disparlure (9), the sex attractant pheromone of the female gypsy moth. This transformation represents a formal asymmetric epoxidation across a nonfunctionalized olefin, not a direct option with traditional Sharpless asymmetric epoxidation technology. This clever variation using initial Sharpless dihydroxylation (applicable to nonfunctionalized olefins) and subsequent epoxide formation is starting to be recognized as a useful indirect method for asymmetric epoxidation. 

In a recent presentation, Cameron (564) once again summarized the promises and problems of the field work with disparlure We do need more time for testing—BUT—we do not need any large scale tests in 1978. If this approach is to be pursued, emphasis in 1978 tests should be directed to formulation development and rates of lure release.. .. ... 

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