Retro-Baeyer-Villiger oxidation

In einer Art Retro-Baeyer-Villiger-Oxidation konnen aus Carbonsaure-estern mit Lithium-naphthalin bis zu 50% der entsprechenden Ketone entstehen. Als Nebenpro-dukte bilden sich infolge Dimerisierung 1,2-Diketone3. 

The conversion of 119 to retro-aldol substrate 121 was accomplished by hydrolysis of the acetal and esterification of the resulting acid to give 120. This process was accompanied by epimerization of both the ester and the resulting methyl ketone, presumably to relieve strain. Baeyer-Villiger oxidation of 120 completed the transformation to 121. The sensitive aldehyde was then converted to 122 using chemistry analogous to that developed by the Woodward group. The bottom line is that this is a creative plan that had trouble when it came to the details (tactics). 

The Baeyer-Villiger oxidation of 7-oxabicyclo[2.2.1]heptan-2-ones is the most used reaction to cleave a C-C bond of the 7-oxabicyclo[2.2.1]heptanes. Other routes have used retro-Claisen, retro-Diekmann, and Grob fragmentations. They have been reviewed elsewhere [11]. Enoxysilanes derived from 7-oxanorboman-2-ones can be ozonolyzed into 2,5-anhydrouronic acid derivatives, precursors for C-nucleosides [225]. 

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