Enamines Simmons-Smith reaction

The Simmons-Smith reaction has been used as the basis of a method for the indirect a methylation of a ketone. The ketone (illustrated for cyclohexanone) is first converted to an enol ether, an enamine (16-12) or silyl enol ether (12-22) and cyclopropanation via the Simmons-Smith reaction is followed by hydrolysis to give a methylated ketone. A related procedure using diethylzinc and diiodomethane allows ketones to be chain extended by one carbon. In another variation, phenols can be ortho methylated in one laboratory step, by treatment with Et2Zn and... 

Chloroiodomethane has been used instead of methylene iodide to methylenate cyclic enamines (43). Methylene bromide was applicable to the Simmons-Smith reaction instead of methylene iodide when highly active zinc-copper couple was used 298,558). The resulting BrCH2ZnBr is an effective methylene transfer reagent. 

Aminocyclopropanes were prepared from enamines by the addition of Simmons-Smith reagent (688) or best through the cuprous-chloride-promoted decomposition of diazomethane (689). The reaction of an enamine with chloroform and base and opening of the resultant aminocyclopropane to an ynamine was reported (690). 

A new angular methylation procedure, at Cis, involving the Simmons-Smith reagent was discovered, thus extending the usefulness of the Smith-Torgov total synthesis of 19-norsteroids. The preparation and properties of 5,19-cyclosteroids was the subject of several studies.Interestingly enough, the Villsmeier reaction on enamines of 3-heto-A -steroids led to the 1,6-diformyl derivatives. ... 

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