Conjugate addition-alkylation reactions of lithium dialkyl cuprates to hex-2-enopyrano-4-ulosides (1), hex-3-enopyrano-2-ulosides (2), and hex-1-enopyrano-3-uloses (3) have been investigated. Extensive studies with 1 show that the homogeneous system using the soluble tri-n-butylphosphine copper(I) complex is less satisfactory than the heterogeneous medium in which copper(I) iodide is used. The use of Grignard reagents versus alkyl lithiums has also been investigated, the latter being found preferable. 1,2-Addition was observed in some cases, but conditions were developed to avoid formation of these side products.With α-enones 1 and 2 alkylation is completely stereoselective, the newly introduced alkyl group being in axial orientation. With 3 a complex mixture is obtained from which equatorial and axial adducts can be isolated in approximately equal amounts.