Allylsamarium bromide

Oximes are also good substrates for allylsamarium bromide addition.25 The Beckmann rearrangement product 44 was produced from oxime 43 in good yields when the ratio of allysamarium bromide to oximes was more than 3 1 (Equation (8)). This type of product was also obtained when the other allylic organometallic compounds were used. The reaction mechanism was proposed as shown in Scheme 13. 

Diattylcarbinamines. Allylsamarium bromide formed in situ (Sm + allyl bromide) adds to nitriles to generate the catbinamines (7 examples, 66-81%). 

Butenanddes and 3-butenethioamides A straightforward synthesis of these amides is by addition of allylsamarium bromide to isocyanates and isothiocyanates, respectively. 

Diorganochakogenides. A method for synthesis of allyl sulfides and selenides involves formation of allylsamarium bromide and its reaction with PhX-XPh (X=S, Se) in THF. For a similar approach to benzyl sulfides, the benzylsamarium halides are formed in the presence of BiClj. Aqueous media can be used in this latter reaction. 

The substitution reaction between gsro-diacetates and allylsamarium bromide has also been investigated. Homoallylic alcohol acetates were obtained in moderate to good yields (Scheme 302).1090... 

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