Grignard reagents with oxime sulfonates

Oxime sulfonates were rearranged in the presence of diisobutylaluminum methyl sulfide to produce methylthioimidates, e.g. (291 equation 155), and methylthiolactim ethers in good yields. The adducts formed in the reaction of Grignard reagents with trimethylsilylmethyl isothiocyanate can be alkylated to furnish the -trimethylsilylmethylthioimidates (292 equation 156). 2.603 Ph,... 

If the rearrangement of oxime sulfonates is induced by organoaluminum reagents,the intermediate (71) is captured by the nucleophile originally attached to the Al. By this means an oxime can be converted to an imine, an imino thioether (R—N—C—SR), or an imino nitrile (R—N—C—In the last case, the nucleophile comes from added trimethyl si lyl cyanide. The imine-producing reaction can also be accomplished with a Grignard reagent in benzene or toluene. ... 

Beckmann rearrangement.3 Reaction of oxime sulfonates with simple Grignard reagents in dry toluene at —78° results in imines, which can be reduced to a-alkylamincs or alkylated with allylic or propargylic Grignard reagents to furnish a,a-diulkylnmincs. 

Grignard reagents have also been found to be effective for these types of transformations (equation 24), but not with cyclopentanone oxime sulfonate. ... 

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