Tris Peterson olefination

Prepared by Peterson olefination from tris(trimethylsilyl)methyllithium and the corresponding aldehyde, see ref [39]. 

Peterson olefination reaction. The application to reaction of an /V-(tri methyl silylmethyl) formamidine with carbonyl compounds provides enamines that are use ful for transformation into homologous nitriles via the A/, -dimethylhydrazones. 

A homo-Peterson process intervened upon 1,4-rearrangement of the alkoxide formed by addition of tris(trimethylsilyl)methyllithium 124 to styrene oxide. The resulting carbanion 125 led mainly to the homo-Peterson product 126, with some of the adduct 127 from addition to a second equivalent of the epoxide. In their report, Fleming and co-workers noted that the homo-Peterson reaction is probably favored in this case by the benzylic positioning of the silyloxy group in 125, and they discussed the parallel between the Peterson olefination and a 1,3-Brook rearrangement process. ... 

Metalation of tris(TMS)phosphine with butyllithium, followed by treatment with 2,3-di-f-butylcyclopropenone, and finally addition of excess TMSCl can provide the phosphatria-fulvene 5 in high yield, via a one-pot Peterson-type olefination... 

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