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.
MANUFACTURING METHOD FOR THE ALDEHYDE BY HYDROFORMYLATION REACTION
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Paragraph 0079-0081; 0083-0084; 0101, (2021/07/13)
A phosphine ligand represented by chemical formula 1. Transition metal catalyst A hydroformylation catalyst composition comprising a solvent and a solvent. Provided is a process for preparing aldehydes by hydroformylation using olefinic compounds and formaldehyde to produce aldehydes.
Ligand coordination sphere effect of Schiff base cis-dioxomolybdenum(VI) complexes in selective catalytic oxidation of alcohols
Liu, Haiwen,Zhuo, Zihan,Zhang, Yan,Wei, Hang,Zhang, Wenxin,Li, Tong,Mao, Zuodong,Wang, Weili
, p. 1253 - 1261 (2021/08/13)
Several cis-dioxomolybdenum(VI) complexes with Schiff bases-derived ligands were synthesized and fully characterized. The catalytic performances of these complexes were tested in the alcohol oxidation under solvent-free condition using H2O2 as oxidant giving high results. The influence of the oxygen, sulfur, and nitrogen atom within the coordination sphere around the molybdenum center was studied (S?>?N?>?O). From this study, we suggest that there exists a relationship between the electronegativity of the atom and the catalytic performance in alcohol oxidation.
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.
Synthesis of Enantioenriched Amines by Iron-Catalysed Amination of Alcohols Employing at Least One Achiral Substrate
Bottari, Giovanni,Afanasenko, Anastasiia,Castillo-Garcia, Antonio A.,Feringa, Ben L.,Barta, Katalin
supporting information, p. 5436 - 5442 (2021/06/17)
The synthesis of a broad range of enantioenriched amines by the direct Fe-catalysed coupling of amines with alcohols through the borrowing hydrogen strategy, while at least one of these substrates is achiral is reported. When starting from α-chiral amines and achiral alcohols, a wide range of enantioenriched amine products, including N-heterocyclic moieties can be obtained with complete retention of stereochemistry and the power of this method is demonstrated in the one-step synthesis of known pharmaceuticals from commercially available, simple enantiopure primary amines and achiral alcohols. It was also found that the use of β-branched enantioenriched primary alcohols and achiral amines as reaction partners leads to a partial loss of stereochemical integrity in the final product, however, a systematic optimization enabled partial retention of enantiopurity and possible parameters effecting for racemization were identified. (Figure presented.).
Highly regioselective homogeneous isomerization-hydroformylation of 2-butene with water- and air-stable phosphoramidite bidentate ligand
Tang, Songbai,Jiang, Yanxin,Yi, Jiwei,Duan, Xiaoxia,Fu, Haiyan,Li, Ruixiang,Yuan, Maolin,Chen, Hua,Yang, Chunji,Zheng, Xueli
, (2021/05/10)
Highly selective isomerization-hydroformylation of 2-butene was achieved with the presence of Rh(acac)(CO)2 and a phosphoramidite bidentate ligand which bearing 2,2′-dihydroxy-1,1′-binaphthyl backbone and N-indolyl substitute. The molar ratio of n- to isovaleraldehyde (217) is distinctly higher than the reported systems. NMR and IR revealed that the five-coordinate HRh(ligand)(CO)2 was an equatorial-equatorial configuration which contributed to the n-selectivity of valeraldehyde. The strong π-acceptor ability of ligand was suggested to play a key role in fast isomerization of 2-butene. Hydrolysis and oxidation experiments demonstrated that the ligand was water- and air-stable. Cyclic voltammetry measurement confirmed that this phosphoramidite ligand is more difficult to be oxidized, compared with the phosphine, phosphinite and phosphite ligands. Inspiringly, recycling experiments showed the catalytic system could work for at least 7 runs with unchanged selectivity.
An In-Situ Self-regeneration Catalyst for the Production of Renewable Penta-1,3-diene
Feng, Ruilin,Qi, Yanlong,Liu, Shijun,Cui, Long,Dai, Quanquan,Bai, Chenxi
supporting information, p. 9495 - 9498 (2021/05/27)
Catalyst deactivation is a problem of great concern for many heterogeneous reactions. Here, an urchin-like LaPO4 catalyst was easily developed for pentane-2,3-diol dehydration; it has an impressive ability to restore the activity in situ by itself during the reaction, accounting for its high stability. This facilitates the efficient production of renewable penta-1,3-diene from pentane-2,3-dione via a novel approach, where penta-2,3-diol was obtained as an intermediate in 95 % yield under mild conditions.
Chromium-Catalyzed Production of Diols From Olefins
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Paragraph 0111, (2021/03/19)
Processes for converting an olefin reactant into a diol compound are disclosed, and these processes include the steps of contacting the olefin reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and hydrolyzing the reduced chromium catalyst to form a reaction product comprising the diol compound. While being contacted, the olefin reactant and the supported chromium catalyst can be irradiated with a light beam at a wavelength in the UV-visible spectrum. Optionally, these processes can further comprise a step of calcining at least a portion of the reduced chromium catalyst to regenerate the supported chromium catalyst.
Chemo- And regioselective hydroformylation of alkenes with CO2/H2over a bifunctional catalyst
Hua, Kaimin,Liu, Xiaofang,Wei, Baiyin,Shao, Zilong,Deng, Yuchao,Zhong, Liangshu,Wang, Hui,Sun, Yuhan
supporting information, p. 8040 - 8046 (2021/11/01)
As is well known, CO2 is an attractive renewable C1 resource and H2 is a cheap and clean reductant. Combining CO2 and H2 to prepare building blocks for high-value-added products is an attractive yet challenging topic in green chemistry. A general and selective rhodium-catalyzed hydroformylation of alkenes using CO2/H2 as a syngas surrogate is described here. With this protocol, the desired aldehydes can be obtained in up to 97% yield with 93/7 regioselectivity under mild reaction conditions (25 bar and 80 °C). The key to success is the use of a bifunctional Rh/PTA catalyst (PTA: 1,3,5-triaza-7-phosphaadamantane), which facilitates both CO2 hydrogenation and hydroformylation. Notably, monodentate PTA exhibited better activity and regioselectivity than common bidentate ligands, which might be ascribed to its built-in basic site and tris-chelated mode. Mechanistic studies indicate that the transformation proceeds through cascade steps, involving free HCOOH production through CO2 hydrogenation, fast release of CO, and rhodium-catalyzed conventional hydroformylation. Moreover, the unconventional hydroformylation pathway, in which HCOOAc acts as a direct C1 source, has also been proved to be feasible with superior regioselectivity to that of the CO pathway.
