96-17-3Relevant articles and documents
Production of renewable 1,3-pentadiene over LaPO4 via dehydration of 2,3-pentanediol derived from 2,3-pentanedione
Bai, Chenxi,Cui, Long,Dai, Quanquan,Feng, Ruilin,Liu, Shijun,Qi, Yanlong
, (2022/02/07)
1,3-Pentadiene plays an extremely important role in the production of polymers and fine chemicals. Herein, the LaPO4 catalyst exhibits excellent catalytic performance for the dehydration production of 1,3-pentadiene with 2,3-pentanediol, a C5 diol platform compound that can be easily obtained by hydrogenation of bio-based 2,3-pentanedione. The relationships of catalyst structure-acid/base properties-catalytic performance was established, and an acid-base synergy effect was disclosed for the on-purpose synthesis of 1,3-pentadiene. Thus, a balance between acid and base sites was required, and an optimized LaPO4 with acid/base ratio of 2.63 afforded a yield of 1,3-pentadiene as high as 61.5% at atmospheric pressure. Notably, the Br?nsted acid sites with weak or medium in LaPO4 catalyst can inhibit the occurrence of pinacol rearrangement, resulting in higher 1,3-pentadiene production. In addition, the investigation on reaction pathways demonstrated that the E2 mechanism was dominant in this dehydration reaction, accompanied by the assistance of E1 and E1cb.
Synthesis of Chiral Amines via a Bi-Enzymatic Cascade Using an Ene-Reductase and Amine Dehydrogenase
Fossey-Jouenne, Aurélie,Jongkind, Ewald P. J.,Mayol, Ombeline,Paul, Caroline E.,Vergne-Vaxelaire, Carine,Zaparucha, Anne
, (2021/12/23)
Access to chiral amines with more than one stereocentre remains challenging, although an increasing number of methods are emerging. Here we developed a proof-of-concept bi-enzymatic cascade, consisting of an ene reductase and amine dehydrogenase (AmDH), to afford chiral diastereomerically enriched amines in one pot. The asymmetric reduction of unsaturated ketones and aldehydes by ene reductases from the Old Yellow Enzyme family (OYE) was adapted to reaction conditions for the reductive amination by amine dehydrogenases. By studying the substrate profiles of both reported biocatalysts, thirteen unsaturated carbonyl substrates were assayed against the best duo OYE/AmDH. Low (5 %) to high (97 %) conversion rates were obtained with enantiomeric and diastereomeric excess of up to 99 %. We expect our established bi-enzymatic cascade to allow access to chiral amines with both high enantiomeric and diastereomeric excess from varying alkene substrates depending on the combination of enzymes.
Method for synthesizing fluorescent dye intermediate aldehyde by hydroformylation of 1,3-diene compound
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Paragraph 0053-0054; 0056-0057, (2021/08/07)
The invention discloses a method for synthesizing a fluorescent dye intermediate aldehyde by hydroformylation of 1,3-diene compound. The method comprises the following steps: S1, sequentially adding 0.01 mmol (1 mol%) of [Rh(cod)Cl]2, 0.1 mmol of a phosphine ligand(P/Rh=10/1) and 1 mmol of diene into a reaction flask, adding 1 ml of a solvent DMF, putting the reaction flask into a high-pressure reaction kettle, after the reaction is finished, transferring a mixed solution into a 25 mL glass bottle with 200 microliters of n-tridecane as an internal standard by using a rubber head dropper, and detecting; and S2, determining the product yield and the structure through a gas chromatograph and a nuclear magnetic resonance spectrum, wherein the obtained olefin conversion rate is larger than 99%, the aldehyde yield ranges from 61% to 99%, and the regioselectivity of the product aldehyde ranges from 70/30 to 100/0. According to the method disclosed by the invention, the separation and purification steps of aldehyde products are simplified, and the substrate of the dialkene hydroformylation reaction is excellent in universality.
