3950-21-8Relevant articles and documents
Efficient separation of diastereomeric mixtures of syn - And anti -2,4-pentanediol
Pan, Heqi,Tu, Siyu,Zhang, Chunming,Young, Andrew,Fontaine, Philip P.
, p. 463 - 469 (2015)
A simple and practical process was developed for the efficient separation of diastereomeric syn- and anti-2,4-pentanediol by selective acetalization of a diastereomeric mixture of the 2,4-pentanediols and selective hydrolysis of the corresponding acetals. The process relies upon the reaction rate differences of syn-2,4-pentanediol (syn-diol) and anti 2,4-pentanediol (anti-diol) in acetalization and of the corresponding acetals in hydrolysis: the syn-diol reacts faster to form a more stable acetal than the anti-diol, which in turn is more susceptible to hydrolysis by Bronsted acid. Acetalization of a 2,4-pentanediol diastereomeric mixture (syn/anti = 45:55) with acetophenone (0.95 equiv relative to syn-diol) leads to the formation of a syn-enriched acetal mixture with a syn/anti diastereomeric ratio (drs/a) of 6:1, leaving an anti-enriched diol mixture (drs/a = 1:7). Subsequent kinetic resolution via selective hydrolysis of the minor anti-acetal with a catalytic amount of 1.0 N HCl at ambient temperature affords the pure syn-acetal (drs/a > 99:1) in the organic phase and the anti-enriched 2,4-pentanediols (drs/a = 1:6) in the aqueous phase, which are conveniently separated by a phase cut. Hydrolysis of the syn-acetal is facile in alcohol solvents at elevated temperatures (60-80 °C), yielding the pure syn-diol. A second acetalization of the anti-enriched 2,4-pentanediols leads to the pure anti-2,4-pentanediol. This separation gives the syn-diol in 75-79% yield with drs/a > 99:1 and the anti-diol in 79-85% yield with dra/s > 98:2. Additionally, the acetophenone used for the acetalization can be recovered in 88-92% yield, and therefore, the overall process is high-yielding, atom-economical, and potentially recyclable.
Stereoselective generation of 1,3- and 1,4-dioxy-substituted carbanions by sparteine-assisted deprotonation of chiral precursors: Substrate or reagent control in the synthesis of α, γ- and α,δ-diols
Ahrens, Hartmut,Paetow, Mario,Hoppe, Dieter
, p. 5327 - 5330 (1992)
The deprotonation of a dicarbamate, derived from (S)-butane-1,3-diol, by sec-butyllithium takes an highly diastereoselective, but opposite, direction in the presence of (-)-sparteine and of tetramethylethylenediamine (TMEDA), respectively. The (S)-pentane-1,4-diol derivative shows the same stereochemical preference under both conditions.
Stereoselective methoxyselenenylation of acyclic allylic alcohol derivatives: A method for the synthesis of 1,3-anti-diols
Kim, Kwan Soo,Park, Heung Bok,Kim, Ji Young,Ahn, Yeong Hee,Jeong, In Howa
, p. 1249 - 1252 (1996)
Reaction of secondary acyclic trans-allylic alcohol derivatives with PhSeBr in the presence of 2,6-di-t-butylpyridine in MeOH proceeded in a highly regio- and stereoselective manner and the subsequent reduction and deprotection of the resultant methoxyselenides afforded mostly 1,3-anti-diols. The methoxyselenenylation of the acetate derivative of the same allylic alcohol, on the other hand, gave several other isomers along with the 1,3-anti-diol derivative.
Nagai et al.
, p. 295 (1959)
Synthesis and Applications of (Pyridyl)imine Fe(II) Complexes as Catalysts in Transfer Hydrogenation of Ketones
Kumah, Robert T.,Vijayan, Paranthaman,Ojwach, Stephen O.
, p. 344 - 352 (2020/07/25)
Abstract: Chiral (pyridyl)imine Fe(II) complexes, [Fe(L1)3]2+[PF6?]2, (Fe1), [Fe(L2)3]2+[PF6?]2, (Fe2), [Fe(L3)3]2+[PF6?]2 (Fe3), and [Fe(L4)3]2+[PF6?]2 (Fe4) were synthesised by reactions of synthons (S-)-1-phenyl-N-(pyridine-2-yl) ethylidine)ethanamine (L1), (R-)-1-phenyl-N-(pyridine-2-yl) ethylidine) ethanamine (L2), (S)-1-phenyl-N-(pyridine-2-yl methylene) ethanamine (L3) and (S)-1-phenyl-N-(pyridine-2-yl methylene)ethanamine (L4) with the FeCl2 salt. The solid-state structure of complex Fe4 showed that the?Fe atom contains three units of bidentate bound ligand L4 to form a six-coordinate cationic compound. The Fe(II) complexes were evaluated as catalysts in asymmetric transfer hydrogenation of ketones reactions and showed moderate catalytic activities with low enantioselectivity. Catalytic activities of the respective complexes were regulated by the nature of the metal complexes, ketone substrate and reaction conditions. Mercury and sub-stoichiometric poisoning experiments implicate possible formation of both active Fe(0) nanoparticles and Fe(II) homogeneous intermediates. Graphic Abstract: [Figure not available: see fulltext.]
Method for preparing beta-diol from beta-diketone by hydrogenation
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Paragraph 0041-0044, (2017/02/23)
The invention relates to a method for preparing beta-diol from beta-diketone by hydrogenation. The method comprises the following steps: in the presence of a catalyst and under the fixed-bed hydrotreating reaction condition, enabling beta-diketone to be in contact with hydrogen, so as to obtain beta-diol, wherein the catalyst contains CuO and ZnO, preferably also contains Al2O3, and more preferably also contains alkali metal oxides. According to the method for preparing beta-diol from beta-diketone by hydrogenation, provided by the invention, the technology of continuously producing beta-diol by adopting a fixed bed device is realized, the technology is simple and convenient to operate, the utilization ratio of raw materials and the production efficiency of products are improved, the reaction does not need to be carried out under high pressure, and potential safety hazards are reduced.