334-48-5Relevant academic research and scientific papers
Hydrogenation of Unsaturated Carboxylic Acid Catalyzed by Platinum-Silica Coupled with Alkylsilyl Chloride
Kuno, Hideyuki,Takahashi, Kyoko,Shibagaki, Makoto,Matsushita, Hajime
, p. 3320 - 3322 (1990)
Platinum-silica catalysts coupled with alkylsilyl chloride were prepared for the regioselective hydrogenation of unsaturated compounds.These catalysts were stable in polar solvents.It was found that the carbon-carbon double bond far from a hydrophilic site was more rapidly hydrogenated in this catalyst system.
Retinoic acid biosynthesis catalyzed by retinal dehydrogenases relies on a rate-limiting conformational transition associated with substrate recognition
Bchini, Rapha?l,Vasiliou, Vasilis,Branlant, Guy,Talfournier, Fran?ois,Rahuel-Clermont, Sophie
, p. 78 - 84 (2013)
Retinoic acid (RA), a metabolite of vitamin A, exerts pleiotropic effects throughout life in vertebrate organisms. Thus, RA action must be tightly regulated through the coordinated action of biosynthetic and degrading enzymes. The last step of retinoic acid biosynthesis is irreversibly catalyzed by the NAD-dependent retinal dehydrogenases (RALDH), which are members of the aldehyde dehydrogenase (ALDH) superfamily. Low intracellular retinal concentrations imply efficient substrate molecular recognition to ensure high affinity and specificity of RALDHs for retinal. This study addresses the molecular basis of retinal recognition in human ALDH1A1 (or RALDH1) and rat ALDH1A2 (or RALDH2), through the comparison of the catalytic behavior of retinal analogs and use of the fluorescence properties of retinol. We show that, in contrast to long chain unsaturated substrates, the rate-limiting step of retinal oxidation by RALDHs is associated with acylation. Use of the fluorescence resonance energy transfer upon retinol interaction with RALDHs provides evidence that retinal recognition occurs in two steps: binding into the substrate access channel, and a slower structural reorganization with a rate constant of the same magnitude as the kcat for retinal oxidation: 0.18 vs. 0.07 and 0.25 vs. 0.1 s -1 for ALDH1A1 and ALDH1A2, respectively. This suggests that the conformational transition of the RALDH-retinal complex significantly contributes to the rate-limiting step that controls the kinetics of retinal oxidation, as a prerequisite for the formation of a catalytically competent Michaelis complex. This conclusion is consistent with the general notion that structural flexibility within the active site of ALDH enzymes has been shown to be an integral component of catalysis.
A new method for the protection of carboxylic acids with a triisopropylsiloxymethyl group
Yoshimura, Hikaru,Eto, Kohei,Takahashi, Keisuke,Ishihara, Jun,Hatakeyama, Susumi
, p. 1334 - 1339 (2012)
An effective method for the protection of carboxylic acids with a triisopropylsiloxymethyl (TIPSOCH2) group is described. The reactions of various carboxylic acids with C12H25SCH 2OTIPS in the presence of CuBrs
One-step solvent-free aerobic oxidation of aliphatic alcohols to esters using a tandem Sc-Ru?MOF catalyst
Feng, Tingkai,Li, Conger,Li, Tao,Zhang, Songwei
supporting information, p. 1474 - 1480 (2022/03/08)
Esters are an important class of chemicals in industry. Traditionally, ester production is a multi-step process involving the use of corrosive acids or acid derivatives (e.g. acid chloride, anhydride, etc.). Therefore, the development of a green synthetic protocol is highly desirable. This work reports the development of a metal-organic framework (MOF) supported tandem catalyst that can achieve direct alcohol to ester conversion (DAEC) using oxygen as the sole oxidizing agent under strictly solvent-free conditions. By incorporating Ru nanoparticles (NPs) along with a homogeneous Lewis acid catalyst, scandium triflate, into the nanocavities of a Zr MOF, MOF-808, the compound catalyst, Sc-Ru?MOF-808, can achieve aliphatic alcohol conversion up to 92% with ester selectivity up to 91%. A mechanistic study reveals a unique “via acetal” pathway in which the alcohol is first oxidized on Ru NPs and rapidly converted to an acetal on Sc(iii) sites. Then, the acetal slowly decomposes to release an aldehyde in a controlled manner for subsequent oxidation and esterification to the ester product. To the best of our knowledge, this is the first example of DAEC of aliphatic alcohols under solvent-free conditions with high conversion and ester selectivity.
Combining photoredox catalysis and oxoammonium cations for the oxidation of aromatic alcohols to carboxylic acids
Nandi, Jyoti,Hutcheson, Ellen L.,Leadbeater, Nicholas E.
supporting information, (2020/12/25)
A methodology is reported for converting alcohols to the corresponding carboxylic acids. A dual catalytic system involving a merger of photoredox catalysis and 4-acetamido-TEMPO is employed to carry out this oxidation process.
Atomically Dispersed Co Clusters Anchored on N-doped Carbon Nanotubes for Efficient Dehydrogenation of Alcohols and Subsequent Conversion to Carboxylic Acids
Dong, Zhengping,Fang, Jian,Li, Boyang,Xu, Dan,Zhang, Fengwei,Zhao, Hong,Zhu, Hanghang
, p. 4536 - 4545 (2021/09/22)
The catalytic dehydrogenation of readily available alcohols to high value-added carbonyl compounds is a research hotspot with scientific significance. Most of the current research about this reaction is performed with noble metal-based homogeneous catalysts of high price and poor reusability. Herein, highly dispersed Co-cluster-decorated N-doped carbon nanotubes (Co/N-CNTs) were fabricated via a facile strategy and used for the dehydrogenation of alcohols with high efficiency. Various characterization techniques confirmed the presence of metallic Co clusters with almost atomic dispersion, and the N-doped carbon supports also enhanced the catalytic activity of Co clusters in the dehydrogenation reaction. Aldehydes as dehydrogenation products were further transformed in situ to carboxylic acids through a Cannizzaro-type pathway under alkaline conditions. The reaction pathway of the dehydrogenation of alcohols was clearly confirmed by theoretical calculations. This work should provide an effective and simple approach for the accurate design and synthesis of small Co-clusters catalysts for the efficient dehydrogenation-based transformation of alcohols to carboxylic acids under mild reaction conditions.
Light and oxygen-enabled sodium trifluoromethanesulfinate-mediated selective oxidation of C-H bonds
Fu, Hua,Liu, Can,Liu, Yong,Yang, Haijun,Zhu, Xianjin
supporting information, p. 4357 - 4363 (2020/07/14)
Visible light-induced organic reactions are important chemical transformations in organic chemistry, and their efficiency highly depends on suitable photocatalysts. However, the commonly used photocatalysts are precious transition-metal complexes and elaborate organic dyes, which hamper large-scale production due to high cost. Here, for the first time, we report a novel strategy: light and oxygen-enabled sodium trifluoromethanesulfinate-mediated selective oxidation of C-H bonds, allowing high-value-added aromatic ketones and carboxylic acids to be easily prepared in high-to-excellent yields using readily available alkyl arenes, methyl arenes and aldehydes as materials. The mechanistic investigations showed that the treatment of inexpensive and readily available sodium trifluoromethanesulfinate with oxygen under irradiation of light could in situ form a pentacoordinate sulfide intermediate as an efficient photosensitizer. The method represents a highly efficient, economical and environmentally friendly strategy, and the light and oxygen-enabled sodium trifluoromethanesulfinate photocatalytic system represents a breakthrough in photochemistry. This journal is
Oxidation of aromatic and aliphatic aldehydes to carboxylic acids by Geotrichum candidum aldehyde dehydrogenase
Hoshino, Tomoyasu,Yamabe, Emi,Hawari, Muhammad Arisyi,Tamura, Mayumi,Kanamaru, Shuji,Yoshida, Keisuke,Koesoema, Afifa Ayu,Matsuda, Tomoko
, (2020/07/20)
Oxidation reaction is one of the most important and indispensable organic reactions, so that green and sustainable catalysts for oxidation are necessary to be developed. Herein, biocatalytic oxidation of aldehydes was investigated, resulted in the synthesis of both aromatic and aliphatic carboxylic acids using a Geotrichum candidum aldehyde dehydrogenase (GcALDH). Moreover, selective oxidation of dialdehydes to aldehydic acids by GcALDH was also successful.
Process for the preparation of fatty acids
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Paragraph 0179-0206; 0210-0212, (2020/09/04)
The invention discloses a method for preparing fatty acid. The method comprises the following steps: providing a first reactant which is a furan compound containing an carbonyl group; providing a second reactant which is a compound containing a carboxyl group, an ester group or an anhydride group and can participate in a condensation reaction with the carbonyl group of the first reactant; allowingthe first reactant and the second reactant to participate in a first condensation reaction, and allowing a C=O bond of the carbonyl group of the first reactant to be connected with alpha carbon of the carbonyl group of the second reactant and to be converted into a C=C bond so as to form a condensation product; and carrying out a second-step reaction under hydrogen pressure in the presence of a co-catalytic system of a hydrogenation catalyst and Lewis acid, opening a furan ring of the condensation product, carrying out hydrodeoxygenation at the same time, removing all oxygen except for oxygenin the carboxyl group, and allowing a carbon chain to be saturated so as to obtain the fatty acid.
Catalytic deoxygenation of bio-based 3-hydroxydecanoic acid to secondary alcohols and alkanes
Artz, Jens,Brosch, Sebastian,Golchert, Christiane,Hergesell, Adrian H.,Mensah, Joel B.,Palkovits, Regina
, p. 3522 - 3531 (2020/08/28)
This work comprises the selective deoxygenation of bio-derivable 3-hydroxydecanoic acid to either linear alkanes or secondary alcohols in aqueous phase and H2-atmosphere over supported metal catalysts. Among the screened catalysts, Ru-based systems were identified to be most active. By tailoring the catalyst, the product selectivity could be directed to either secondary alcohols or linear alkanes. In the absence of a Br?nsted acidic additive, 2-nonanol and 3-decanol were accessible with a yield of 79% and 6% respectively, both of which can be used in food and perfume industries as flavoring agents and fragrances. To produce alkanes, we successfully synthesized a bifunctional Ru/HZSM-5 catalyst. The acidic zeolite support facilitated the dehydration of the intermediary formed alcohols to alkenes, while the following hydrogenation occurred at the Ru centers. Thus, full 3-hydroxydecanoic acid deoxygenation to nonane and decane, which are both well-established as diesel and jet fuels, was achieved with up to 72% and 12% yield, respectively.
