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Alkylation of acetylenes - new catalysts

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A fascinating trend over the last couple of years has been the use of organic - rather than organometallic -catalysts for many reactions. Since generally these catalysts are amines or amino acids, which are easier to remove from product (and recycle?) than organometallic species, the potential for large scale use is apparent. We have previously mentioned the work of MacMillan (see J Am Chem Soc 2000, 122, 4243; 9874), List (J Am Chem Soc 2000, 122, 2395; 7386; 9336) and Fu (Acc Chem Res 2000, 33, 412, J Am Chem Soc 2001, 123, 353) in these columns on the use of organic catalysts for Diels-Alder reactions, 1, 3 dipolar cycloadditions, aldol and Mannich reactions. Now the group of List has extended its work to the Michael addition of ketones to nitrolefins (List B et al Org Lett, 2001, 3, 2423). Proline catalyses the addition of cyclohexanone to nitrostyrene in good yield, regio and diastereoselectivity, although the ee's could at best be described as modest (up to 23%). Use of a "vinologous" proline improved ee's to 40% in one case. No doubt future publications will report improved asymmetric catalysts. For a recent review of the asymmetric Michael reaction see Krause N et al.