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Chiral 1,4-diphenylphosphines 5-7 as well as thioether 8 were synthesized from tartrates employing Ley's "BDA" and "Dispoke" methodologies as the key step. Rhodium(I) complexes with 5-7 are efficient catalysts for the asymmetric hydrogenation of beta-substituted enamides and MOM-protected beta-hydroxyl enamides, which furnished chiral amines or beta-amino alcohols with 94-->99% ee. These results indicated that the 1,4-dioxane backbone in the ligands having the general structure 2 played an important role in stabilizing metal-ligand chelate conformation. Higher enantioselectivities with ligand 2 were achieved compared with the analogous ligands having the general structure 1.