Criegee intermediate synthesis

In the laboratory of Y. Takemoto, the asymmetric total synthesis of the marine metabolite, halicholactone was accomplished. One advanced intermediate contained a 1,2-vicinal diol moiety which was cleaved under mild conditions to afford the corresponding aldehyde. The Criegee oxidation was chosen to effect this transformation at low temperature, followed by the stereoselective allylation of the resulting aldehyde with tetraallyltin. 

In the synthesis of angular triquinane ( )-silphinene by S. Yamamura et al., the Criegee oxidation was used to obtain a key bicyclic intermediate. ... 

Other preparative methods make use of cyclobutadiene intermediates which react with acetylene compounds. The first method was reported by Criegee and his coworker 6) who prepared tetramethylcyclobutadiene from the 1,2-diiodo derivative (4). In the second method, the cyclobutadiene irontricarbonyl complex is oxidized by Ce,v to produce free cyclobutadiene (5) 7). This reaction is widely used for the synthesis of cyclobutadiene. 

The synthesis of AA by ozonolysis of OA or ricinoleic acid is known since the beginning of the twentieth century [15-17]. The key intermediates and products of the method are in accordance with the still-accepted mechanism developed by Criegee [18] (Scheme 20.1). 

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