Synthesis of Tetrasubstituted Ozonides by the Griesbaum Coozonolysis Reaction:  Diastereoselectivity and Functional Group Transformations by Post-Ozonolysis Reactions

The diastereoselectivity of the Griesbaum coozonolysis reaction with O-methyl 2-adamantanone oxime and 4-substituted cyclohexanones reveals that the major tetrasubstituted ozonide isomers possess cis configurations, suggesting a preferred axial attack of the carbonyl oxide on the cyclohexanone dipolarophiles. It is evident that these tetrasubstituted ozonides are quite stable to triphenylphosphine, borohydrides, hydrazine, alkyllithiums, Grignard reagents, mercaptides, and aqueous KOH as illustrated by the synthesis of amine, alcohol, acid, ester, ether, sulfide, sulfone, and heterocycle-functionalized ozonides by a wide range of post-ozonolysis transformations.