In the exploration of organocuprate reactions, we found that 2,3-dichloropropene conveniently oxidized Me2CuI Li to give Me4CuIII Li and allene as products, equation 1. Taking advantage of this observation, we are developing a new procedure for preparing substituted allenic products from ketone and aldehyde starting materials. This reaction sequence is shown below, equation 2.            The Horner-Wadsworth-Emmons modification of the Ramirez Olefination was used to generate good yields of gem-dibromoalkenes. Metal-halogen exchange followed by treatment with an aldehyde produced an allylic alcohol which was acylated with acetic anhydride to produce the allene precursor. Preliminary studies of this methodology indicate that the reaction produces good yields of the allene. 

New methodology for generating allene analogs

239th National Meeting (2010)

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