Ozonolysis dimethyl sulfide - workup

The major synthetic problem associated with the synthesis of compounds such as NK-104 is the stereoselective construction of the lactone moiety and its connection to an aromatic or ethylenic core. This has been overcome by Minami and colleagues with the enantioselective synthesis of methyl 6-oxo-3,5-isopropylidenehexanoate (52) by ozonolysis of the ester 53, followed by reductive workup using dimethyl sulfide (Scheme 11,14).54 With the required aldehyde 52 now formed, further reaction could permit the production of NK-104 51 to take place enantioselectively. 

One method for the synthesis of hydroxyalkyl-substituted P-lactams is by the Staudinger reaction, the most frequently used method for the synthesis of P-lactams.86 This method for the preparation of 4-acetoxy- and 4-formyl-substituted P-lactams involves the use of diazoketones prepared from amino acids. These diazoketones are precursors for ketenes, in a diastereoselective, photochemically induced reaction to produce exclusively tram-substituted P-lactams. The use of cinnamaldimines 96, considered as vinylogous benzaldimines, resulted in the formation of styryl-substituted P-lactams. Ozonolysis, followed by reductive workup with dimethyl sulfide, led to the formation of the aldehyde 97, whereas addition of trimethyl orthoformate permitted the production of the dimethyl acetal 98 (Scheme 11.26). 

In the preparation of aldehydes by ozonolysis of alkenes, it is important to add the correct amount of ozone to the solution because an excess of O3 can lead to side reactions. Ozonolysis in alcoholic solvents traps the carbonyl oxide as a hydroperoxide. Dimethyl sulfide reduces hydroperoxides under very mild conditions and generates the corresponding aldehydes in excellent yields. This workup procedure is recommended when the aldehyde is the desired reaction product. 

Ozonolysis of carbamate 169 and successive workup with dimethyl sulfide, followed by cyclization with formic acid, yielded hexahydro-3//-... 

What products would you expect to obtain if caryophyllene were subjected to ozonolysis followed by workup with dimethyl sulfide ... 

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