New syntheses are described of 5-hydroxypentane-2,3-dione (7) (i.e., laurencione [Formula: see text]) and of 3-amino-1-hydroxypropan-2-one (3-amino-1-hydroxyacetone) (5) hydrochloride, putative precursors of the C5 unit, C-2′,2,3,4,4′, and of the C3N unit, N-1,C-6,5,5′, respectively, of pyridoxine (6). Keywords: 3-amino-1-hydroxyacetone, 3-amino-1-hydroxypropanone, 5-hydroxypentane-2,3-dione, laurencione, vitamin B6.