24472-75-1Relevant academic research and scientific papers
Dihydroxyacetone phosphate, DHAP, in the crystalline state: monomeric and dimeric forms
?lepokura, Katarzyna,Lis, Tadeusz
scheme or table, p. 512 - 529 (2010/04/27)
It was shown that dihydroxyacetone phosphate may exist in both monomeric DHAP (C3H7O6P) and dimeric DHAP-dimer (C6H14O12P2) form. Monomeric DHAP was obtained in the form of four crystalline salts: CaCl(DHAP)·2.9H2O (7a), Ca2Cl3(DHAP)·5H2O (7b), CaCl(DHAP)·2H2O (7c), and CaBr(DHAP)·5H2O (7d) by crystallization from aqueous solutions containing DHAP acid and CaCl2 or CaBr2, or by direct crystallization from a solution containing DHAP precursor and CaCl2. At least one of the salts is stable and may be stored in the crystalline state at room temperature for several months. The dimeric form was obtained by slow saturation of free DHAP syrup with ammonia at -18 °C and isolated in the form of its hydrated diammonium salt (NH4)2(DHAP-dimer)·4H2O (8). The synthesis of the compounds, their crystallization, and crystal structures determined by X-ray crystallography are described. In all 7a-d monomeric DHAP exists in the monoanionic form in an extended (in-plane) cisoid conformation, with both hydroxyl and ester oxygen atoms being synperiplanar to the carbonyl O atom. The crucial structural feature is the coordination manner, in which the terminal phosphate oxygen atoms act as chelating as well as bridging atoms for the calcium cations. Additionally, the DHAP monoanions chelate another Ca2+ by the α-hydroxycarbonyl moiety, in a manner observed previously in dihydroxyacetone (DHA) calcium chloride complexes. In dimeric 8 the anion is a trans isomer with the dioxane ring in a chair conformation with the hydroxyl groups in axial positions and the phosphomethyl group in an equatorial position.
A novel efficient synthesis of dihydroxyacetone phosphate and bromoacetol phosphate for use in enzymatic aldol syntheses
Gefflaut, Thierry,Lemaire, Marielle,Valentin, Marie-Lise,Bolte, Jean
, p. 5920 - 5922 (2007/10/03)
Dihydroxyacetone phospate (DHAP,7) and bromoacetol phospate (BAP,6) were synthesized in four and five steps, respectively, starting from 1,3- dibromoacetone (2). The key step involves desymetrization and ketone protection of 2 to prepare alcohol 3. Phosphorylation of 3 followed by hydrogenolysis and then deprotection of the ketal function afforded 6. A solution of 7 was prepared after treatment of 6 with NaOH. This route allows a short and convenient preparation of DHAP in large scale and high purity for application to the synthesis of sugar derivatives and preparation of BAP for triosephosphate isomerase inhibition.
