The first direct asymmetric synthesis of anti,anti vinylic 3-amino-1,2-diols from aldehydes is described via a one-pot sequential L-proline catalyzed α-amination/benzoyloxyallylation protocol. The reaction proceeds with exceptionally high diastereoselectivity (>99%) as can be explained based on the Felkin–Ahn transition state model. Its effectiveness is proven unambiguously by demonstrating a short asymmetric synthesis of D-ribo-phytosphingosine tetraacetate (93% ee).