cas 98737-29-2, (2S,3S)-1,2-Epoxy-3-(boc-amino)-4-phenylbutane

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Synthesis method of (2S, 3S)-3-(t-butyloxycarboryl amino)-1, 2-epoxy-4-phenylbutane
The invention relates to the technical field of synthesis of drug intermediates, in particular to a synthesis method of (2S, 3S)-3-(t-butyloxycarboryl amino)-1, 2-epoxy-4-phenylbutane. The method comprises the following steps: condensing N-t-butyloxycarboryl-L-phenylalanine serving as a raw material with substituted phenol under the action of a condensing agent to obtain active ester 15; reacting the active ester 15 with a ylide reagent and alkali to obtain a sulfoxide ylide intermediate 16; reacting the sulfoxide ylide intermediate 16 with halide salt under the action of a catalyst to obtain a halogenated ketone intermediate 6; reducing the halogenated ketone intermediate 6 through a reducing agent under the action of a catalyst to obtain a halogenated methanol intermediate 7; and removing halogen acid from the halogenated methanol intermediate 7 under the action of alkali, and carrying out condensation cyclization to obtain the target product (2S, 3S)-3-(t-butyloxycarboryl amino)-1, 2-epoxy-4-phenylbutane. The synthesis method of the (2S, 3S)-3-(t-butyloxycarboryl amino)-1, 2-epoxy-4-phenylbutane, provided by the invention, has the characteristics of cheap and easily available initial raw materials, safe and controllable process and easiness in operation.
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Paragraph 0043; 0048; 0049; 0054

(2021/06/23)

Aerobic epoxidation of styrene over Zr-based metal-organic framework encapsulated transition metal substituted phosphomolybdic acid
Catalytic epoxidation of styrene with molecular oxygen is regarded as an eco-friendly alternative to producing industrially important chemical of styrene oxide (STO). Recent efforts have been focused on developing highly active and stable heterogeneous catalysts with high STO selectivity for the aerobic epoxidation of styrene. Herein, a series of transition metal monosubstituted heteropolyacid compounds (TM-HPAs), such as Fe, Co, Ni or Cu-monosubstituted HPA, were encapsulated in UiO-66 frameworks (denoted as TM-HPA@UiO-66) by direct solvothermal method, and their catalytic properties were investigated for the aerobic epoxidation of styrene with aldehydes as co-reductants. Among them, Co-HPA@UiO-66 showed relatively high catalytic activity, stability and epoxidation selectivity at very mild conditions (313 K, ambient pressure), that can achieve 82 % selectivity to STO under a styrene conversion of 96 % with air as oxidant and pivalaldehyde (PIA) as co-reductant. In addition, the hybrid composite catalyst can also efficiently catalyze the aerobic epoxidation of a variety of styrene derivatives. The monosubstituted Co atoms in Co-HPA@UiO-66 are the main active sites for the aerobic epoxidation of styrene with O2/PIA, which can efficiently converting styrene to the corresponding epoxide through the activation of the in-situ generated acylperoxy radical intermediate.
Hu, Dianwen,Song, Xiaojing,Zhang, Hao,Chang, Xinyu,Zhao, Chen,Jia, Mingjun
(2021/04/19)

Combining photoredox catalysis and oxoammonium cations for the oxidation of aromatic alcohols to carboxylic acids
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.
Nandi, Jyoti,Hutcheson, Ellen L.,Leadbeater, Nicholas E.
supporting information

(2020/12/25)

Heterogeneous vanadium-catalyzed oxidative cleavage of olefins for sustainable synthesis of carboxylic acids
The development of green and sustainable processes to synthesize active pharmaceutical ingredients and key starting materials is a priority for the pharmaceutical industry. A green and sustainable protocol for the oxidative cleavage of olefins to produce pharmaceutically and biologically valuable carboxylic acids is achieved. The developed protocol involves 70% aq. TBHP as an oxidant over a heterogeneous vanadium catalyst system. Notably, the synthesis of industrially important azelaic acid from various renewable vegetable oils is accomplished. The catalyst could be recycled for up to 5 cycles without significant loss in yield and the protocol was successfully demonstrated at the gram-scale.
Upadhyay, Rahul,Rana, Rohit,Sood, Aakriti,Singh, Vikash,Kumar, Rahul,Srivastava, Vimal Chandra,Maurya, Sushil K.
supporting information
p. 5430 - 5433
(2021/06/09)

1,2-Dibutoxyethane-Promoted Oxidative Cleavage of Olefins into Carboxylic Acids Using O2 under Clean Conditions
Herein, we report the first example of an effective and green approach for the oxidative cleavage of olefins to carboxylic acids using a 1,2-dibutoxyethane/O2 system under clean conditions. This novel oxidation system also has excellent functional-group tolerance and is applicable for large-scale synthesis. The target products were prepared in good to excellent yields by a one-pot sequential transformation without an external initiator, catalyst, and additive.
Ou, Jinhua,Tan, Hong,He, Saiyu,Wang, Wei,Hu, Bonian,Yu, Gang,Liu, Kaijian
p. 14974 - 14982
(2021/10/25)

Merging N-Hydroxyphthalimide into Metal-Organic Frameworks for Highly Efficient and Environmentally Benign Aerobic Oxidation
Two highly efficient metal-organic framework catalysts TJU-68-NHPI and TJU-68-NDHPI have been successfully synthesized through solvothermal reactions of which the frameworks are merged with N-hydroxyphthalimide (NHPI) units, resulting in the decoration of pore surfaces with highly active nitroxyl catalytic sites. When t-butyl nitrite (TBN) is used as co-catalyst, the as-synthesized MOFs are demonstrated to be highly efficient and recyclable catalysts for a novel three-phase heterogeneous oxidation of activated C?H bond of primary and secondary alcohols, and benzyl compounds under mild conditions. Based on the high efficiency and selectivity, an environmentally benign system with good sustainability, mild conditions, simple work-up procedure has been established for practical oxidation of a wide range of substrates.
Wang, Man,Liang, Gan,Wang, Yunhao,Fan, Tao,Yuan, Baoling,Liu, Mingxian,Yin, Ying,Li, Liangchun
supporting information
p. 9674 - 9685
(2021/06/09)

An aerobic oxidation of alcohols into carbonyl synthons using bipyridyl-cinchona based palladium catalyst
We have reported an aerobic oxidation of primary and secondary alcohols to respective aldehydes and ketones using a bipyridyl-cinchona alkaloid based palladium catalytic system (PdAc-5) using oxygen at moderate pressure. ThePdAc-5catalyst was analysed using SEM, EDAX, and XPS analysis. The above catalytic system is used in experiments for different oxidation systems which include different solvents, additives, and bases which are cheap, robust, non-toxic, and commercially available on the industrial bench. The obtained products are quite appreciable in both yield and selectivity (70-85%). In addition, numerous important studies, such as comparisons with various commercial catalysts, solvent systems, mixture of solvents, and catalyst mole%, were conducted usingPdAc-5. The synthetic strategy of oxidation of alcohol into carbonyl compounds was well established and all the products were analysed using1H NMR,13CNMR and GC-mass analyses.
Cheedarala, Ravi Kumar,Chidambaram, Ramasamy R.,Siva, Ayyanar,Song, Jung Il
p. 32942 - 32954
(2021/12/02)

Continuous production method of benzoic acid derivative
The invention relates to the technical field of preparation of benzoic acid derivatives. The invention particularly relates to a continuous production method of a benzoic acid derivative. The continuous reaction device is characterized by comprising a small-diameter sleeve, wherein the small-diameter sleeve is sleeved with a large-diameter sleeve, and a small pipeline is arranged between the small-diameter sleeve and the large-diameter sleeve, and a plurality of small holes are arranged on the small pipeline. The small-diameter casing is rotated, the large-diameter casing is fixed, and the reaction liquid composed of the nitric acid and the toluene derivative is between a small-diameter casing pipe and a large-diameter casing pipe.
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Paragraph 0032-0033; 0035

(2021/11/14)

Photo-induced deep aerobic oxidation of alkyl aromatics
Oxidation is a major chemical process to produce oxygenated chemicals in both nature and the chemical industry. Presently, the industrial manufacture of benzoic acids and benzene polycarboxylic acids (BPCAs) is mainly based on the deep oxidation of polyalkyl benzene, which is somewhat suffering from environmental and economical disadvantage due to the formation of ozone-depleting MeBr and corrosion hazards of production equipment. In this report, photo-induced deep aerobic oxidation of (poly)alkyl benzene to benzene (poly)carboxylic acids was developed. CeCl3 was proved to be an efficient HAT (hydrogen atom transfer) catalyst in the presence of alcohol as both hydrogen and electron shuttle. Dioxygen (O2) was found as a sole terminal oxidant. In most cases, pure products were easily isolated by simple filtration, implying large-scale implementation advantages. The reaction provides an ideal protocol to produce valuable fine chemicals from naturally abundant petroleum feedstocks. [Figure not available: see fulltext.].
Wang, Chang-Cheng,Zhang, Guo-Xiang,Zuo, Zhi-Wei,Zeng, Rong,Zhai, Dan-Dan,Liu, Feng,Shi, Zhang-Jie
p. 1487 - 1492
(2021/07/10)

Bimetallic oxide nanoparticles confined in ZIF-67-derived carbon for highly selective oxidation of saturated C–H bond in alkyl arenes
Zeolite imidazolate frameworks (ZIFs) have recently emerged as an ideal type of carbon precursors with abundant tailorability. In this work, a series of ZIF-derived porous carbon catalysts have been prepared with encapsulation of bimetallic oxide nanoparticles via simple thermal treatment. The composition and structure of these catalysts were confirmed in detail by different characterization methods. The bimetallic oxide (Mn/Co, Fe/Co, and Cu/Co) nanoparticles were encapsulated in the nitrogen-doped graphitized carbon matrix. Moreover, the hierarchically porous structure and carbon defects were successfully constructed in the carbon catalysts. Additionally, in the selective oxidation of saturated C–H bonds in alkyl arenes, the carbon catalysts demonstrate outstanding performance for the oxidation of C–H bonds to corresponding carboxyl groups. This was due to their unique structure can greatly promote mass transfer and molecular oxygen activation, resulting in high conversion and high selectivity. Remarkably, this work here could also provide a novel strategy to the controllable synthesis of metal–organic frameworks (MOFs)-derived carbon catalysts for enhanced performance in heterogeneous catalysis.
Huang, Cheng,Su, Xiaoyan,Gu, Xiangyu,Liu, Rui,Zhu, Hongjun
(2020/10/15)

Isotruxene-based porous polymers as efficient and recyclable photocatalysts for visible-light induced metal-free oxidative organic transformations
Two new isotruxene-based porous polymers were prepared and demonstrated to be highly efficient, metal-free heterogeneous photocatalysts for oxidative transformations using air as the mild oxidant under visible-light irradiation. Both catalysts show excellent recyclability. In addition, the reactions can be performed in water, further indicating the greenness of this method. This journal is
Zhang, Haowen,Zhang, Xiao,Zheng, Ying,Zhou, Cen
supporting information
p. 8878 - 8885
(2021/11/27)

One-Pot Direct Oxidation of Primary Amines to Carboxylic Acids through Tandem ortho-Naphthoquinone-Catalyzed and TBHP-Promoted Oxidation Sequence
Biomimetic oxidation of primary amines to carboxylic acids has been developed where the copper-containing amine oxidase (CuAO)-like o-NQ-catalyzed aerobic oxidation was combined with the aldehyde dehydrogenase (ALDH)-like TBHP-mediated imine oxidation protocol. Notably, the current tandem oxidation strategy provides a new mechanistic insight into the imine intermediate and the seemingly simple TBHP-mediated oxidation pathways of imines. The developed metal-free amine oxidation protocol allows the use of molecular oxygen and TBHP, safe forms of oxidant that may appeal to the industrial application.
Kim, Hun Young,Oh, Kyungsoo,Si, Tengda
supporting information
p. 18150 - 18155
(2021/12/09)

Kinetic study on the reaction of p-tert-butylbenzoic acid with methanol catalyzed by deep eutectic solvent based on choline chloride
The synthesis of methyl p-tert-butylbenzoate using deep eutectic solvent (DES) as a green catalyst was studied in this work. Four DESs were prepared by combining choline chloride (ChCl) and p-toluenesulfonic acid monohydrate (PTSA) with different molar ratios (1:1–3). It was found that ChCl-1.5PTSA with a molar ratio of 1:1.5 was superior to other DESs both in physical properties and catalytic performance. Therefore, it was selected to carry out the kinetic experiments. The effects of stirring speed, temperature, molar ratio of methanol to p-tert-butylbenzoic acid, and catalyst loading on the conversion of p-tert-butylbenzoic acid were discussed. In addition, the reaction kinetics of p-tert-butylbenzoic acid and methanol with ChCl-1.5PTSA as catalyst was explored in the temperature range of 332.15–349.15 K, and the experimental data were well fitted by pseudo-homogeneous model. Moreover, the recyclability of ChCl-1.5PTSA was evaluated. The result shows that the catalyst could be easily separated from the reaction system without any extractant, and the performance of the catalyst remains stable in multiple times recycling. Therefore, ChCl-1.5PTSA is expected to be an efficient and environmentally friendly catalyst for the methyl esterification of p-tert-butylbenzoic acid with a bright future in industrial application.
Guo, Yuan,Tang, Linmao,Xue, Weilan,Zeng, Zuoxiang
p. 1241 - 1252
(2021/08/12)

Aerobic oxidative C?C bond cleavage of aromatic alkenes by a high valency iron-containing perovskite catalyst
High valency iron-containing perovskite catalyst BaFeO3-dcould efficiently promote the additive-free oxidative C?C bond cleavage of various aromatic alkenes to the corresponding aldehydes or ketones using O2as the sole oxidant. This system was applicable to the gram-scale oxidation of 1,1-diphenylethylene, in which 2.71 g (75% yield) of the analytically pure ketone could be isolated.
Shibata, Satomi,Kamata, Keigo,Hara, Michikazu
p. 2369 - 2373
(2021/04/22)

Hydrolysis of amides to carboxylic acids catalyzed by Nb2O5
Hydrolysis of amides to carboxylic acids is an industrially important reaction but is challenging due to the difficulty of cleaving the resonance stabilized amidic C-N bond. Twenty-three heterogeneous and homogenous catalysts were examined in the hydrolysis of acetamide. Results showed that Nb2O5was the most effective heterogeneous catalyst with the greatest yield of acetic acid. A series of Nb2O5catalysts calcined at various temperatures were characterized and tested in the hydrolysis of acetamide to determine the effects of crystal phase and surface properties of Nb2O5on catalytic performance. The high catalytic performance observed was attributed mainly to the facile activation of the carbonyl bond by Lewis acid sites that function even in the presence of basic inhibitors (NH3and H2O). The catalytic studies showed the synthetic advantages of the present method, such as simple operation, catalyst recyclability, additive free, solvent free, and wide substrate scope (>40 examples; up to 95% isolated yield).
Siddiki,Rashed, Md. Nurnobi,Touchy, Abeda Sultana,Jamil, Md. A. R.,Jing, Yuan,Toyao, Takashi,Maeno, Zen,Shimizu, Ken-Ichi
p. 1949 - 1960
(2021/03/26)

Preparation of hexafluoroisopropyl esters by oxidative esterification of aldehydes using sodium persulfate
A simple, metal-free route for the oxidative esterification of aldehydes to yield hexafluoroisopropyl esters is reported. The methodology employs sodium persulfate and a catalytic quantity of a nitroxide and is applicable to aromatic, heteroaromatic, and aliphatic aldehydes.
León Sandoval, Arturo,Politano, Fabrizio,Witko, Mason L.,Leadbeater, Nicholas E.
supporting information
p. 2986 - 2990
(2021/04/14)

Cleavage of Carboxylic Esters by Aluminum and Iodine
A one-pot procedure for deprotecting carboxylic esters under nonhydrolytic conditions is described. Typical alkyl carboxylates are readily deblocked to the carboxylic acids by the action of aluminum powder and iodine in anhydrous acetonitrile. Cleavage of lactones affords the corresponding ω-iodoalkylcarboxylic acids. Aryl acetylates undergo deacetylation with the participation of the neighboring group. This method enables the selective cleavage of alkyl carboxylic esters in the presence of aryl esters.
Sang, Dayong,Yue, Huaxin,Fu, Yang,Tian, Juan
p. 4254 - 4261
(2021/03/09)

Cobalt-Catalyzed Acceptorless Dehydrogenation of Alcohols to Carboxylate Salts and Hydrogen
The facile oxidation of alcohols to carboxylate salts and H2 is achieved using a simple and readily accessible cobalt pincer catalyst (NNNHtBuCoBr2). The reaction follows an acceptorless dehydrogenation pathway and displays good functional group tolerance. The amine-amide metal-ligand cooperation in cobalt catalyst is suggested to facilitate this transformation. The mechanistic studies indicate that in-situ-formed aldehydes react with a base through a Cannizzaro-type pathway, resulting in potassium hemiacetolate, which further undergoes catalytic dehydrogenation to provide the carboxylate salts and H2
Gunanathan, Chidambaram,Kishore, Jugal,Pattanaik, Sandip,Pradhan, Deepak Ranjan
supporting information

(2020/03/03)

Green synthesis method of aromatic acid
The invention discloses a green synthesis method of aromatic acid. Nickel-catalyzed carbonyl insertion is carried out on aryl iodine in the presence of formate, acid anhydride, a phosphine ligand andan organic solvent by using a nickel catalyst to obtain the aromatic acid. Efficient catalytic conversion is realized by utilizing the cheap nickel catalyst, the reaction conditions are mild, and theoperation is simple.
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Paragraph 0048-0122; 0147-0152; 0271-0272

(2020/05/01)

Photoinduced Carbon Tetrabromide Initiated Aerobic Oxidation of Substituted Toluenes to Carboxylic Acids
A mild and metal-free procedure is reported for the aerobic oxidation of substituted toluenes to carboxylic acids by using CBr 4 as initiator under irradiation from a 400 nm blue light-emitting diode.
Li, Xiaoqing,Xu, Xiangsheng,Yan, Xiaoyu,Yan, Xinhuan,Zhang, Guofu,Zheng, Kun
p. 272 - 274
(2020/02/18)

Essential oil-based design and development of novel anti-Candida azoles formulation
Candida is the most common fungal class, causing both superficial and invasive diseases in humans. Although Candida albicans is the most common cause of fungal infections in humans, C. auris is a new emergent serious pathogen causing complications similar to those of C. albicans. Both C. albicans and C. auris are associated with high mortality rates, mainly because of their multidrug-resistance patterns against most available antifungal drugs. Although several compounds were designed against C. albicans, very few or none were tested on C. auris. Therefore, it is urgent to develop novel effective antifungal drugs that can accommodate not only C. albicans, but also other Candida spp., particularly newly emergent one, including C. auris. Inspired by the significant broad-spectrum antifungal activities of the essential oil cuminaldehyde and the reported wide incorporation of azoles in the antifungal drugs, a series of compounds (UoST1-11) was designed and developed. The new compounds were designed to overcome the toxicity of the aldehyde group of cuminaldehyde and benefit from the antifungal selectivity of azoles. The new developed UoST compounds showed significant anti-Candida activities against both Candida species. The best candidate compound, UoST5, was further formulated into polymeric nanoparticles (NPs). The new formula, UoST5-NPs, showed similar activities to the nanoparticles-free drug, while providing only 25% release after 24 h, maintainng prolonged activity up to 48 h and affording no toxicity. In conclusion, new azole formulations with significantly enhanced activities against C. albicans and C. auris, while maintaining prolonged action and no toxicities at lower concentrations, were developed.
Fayed, Bahgat,Haider, Mohamed,Hamdy, Rania,Hamoda, Alshaimaa M.,Rawas-Qalaji, Mutasem,Soliman, Sameh S. M.
(2020/04/10)

Selective inhibition of Rhizopus eumelanin biosynthesis by novel natural product scaffold-based designs caused significant inhibition of fungal pathogenesis
Melanin is a dark color pigment biosynthesized naturally in most living organisms. Fungal melanin is a major putative virulence factor of Mucorales fungi that allows intracellular persistence by inducing phagosome maturation arrest. Recently, it has been shown that the black pigments of Rhizopus delemar is of eumelanin type, that requires the involvement of tyrosinase (a copper-dependent enzyme) in its biosynthesis. Herein, we have developed a series of compounds (UOSC-1-14) to selectively target Rhizopus melanin and explored this mechanism therapeutically. The compounds were designed based on the scaffold of the natural product, cuminaldehyde, identified from plant sources and has been shown to develop non-selective inhibition of melanin production. While all synthesized compounds showed significant inhibition of Rhizopus melanin production and limited toxicity to mammalian cells, only four compounds (UOSC-1, 2, 13, and 14) were selected as promising candidates based on their selective inhibition to fungal melanin. The activity of compound UOSC-2 was comparable to the positive control kojic acid. The selected candidates showed significant inhibition of Rhizopus melanin but not human melanin by targeting the fungal tyrosinase, and with an IC50 that are 9 times lower than the reference standard, kojic acid. Furthermore, the produced white spores were phagocytized easily and cleared faster from the lungs of infected immunocompetent mice and from the human macrophages when compared with wild-type spores. Collectively, the results suggested that the newly designed derivatives, particularly UOSC-2 can serve as promising candidate to overcome persistence mechanisms of fungal melanin production and hence make them accessible to host defenses.
Soliman, Sameh S.M.,Hamdy, Rania,Elseginy, Samia A.,Gebremariam, Teclegiorgis,Hamoda, Alshaimaa M.,Madkour, Mohamed,Venkatachalam, Thenmozhi,Ershaid, Mai N.,Mohammad, Mohammad G.,Chamilos, Georgios,Ibrahim, Ashraf S.
p. 2489 - 2507
(2020/09/02)

Oxidation of aromatic and aliphatic aldehydes to carboxylic acids by Geotrichum candidum aldehyde dehydrogenase
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.
Hoshino, Tomoyasu,Yamabe, Emi,Hawari, Muhammad Arisyi,Tamura, Mayumi,Kanamaru, Shuji,Yoshida, Keisuke,Koesoema, Afifa Ayu,Matsuda, Tomoko
(2020/07/20)

Cobalt-catalyzed carboxylation of aryl and vinyl chlorides with CO2
The transition-metal-catalyzed carboxylation of aryl and vinyl chlorides with CO2 is rarely studied, and has been achieved only with a Ni catalyst or combination of palladium and photoredox. In this work, the cobalt-catalyzed carboxylation of aryl and vinyl chlorides and bromides with CO2 has been developed. These transformations proceed under mild conditions and exhibit a broad substrate scope, affording the corresponding carboxylic acids in good to high yields.
Wang, Yanwei,Jiang, Xiaomei,Wang, Baiquan
supporting information
p. 14416 - 14419
(2020/12/01)

Palladium-catalyzed carbonylative synthesis of acylstannanes from aryl iodides and hexamethyldistannane
In this communication, we describe a new method for the carbonylative synthesis of acylstannanes from aryl iodides and hexamethyldistannane. With Pd(PPh3)4 as the catalyst and toluene as the solvent at 60 °C under 10 bar CO for 16 h, the desired acylstannanes were obtained in good to excellent yields. In order to facilitate isolation and analysis, the obtained acylstannanes were transformed into the corresponding benzoic acids by simply stirring under air for 5 h.
Chen, Bo,Franke, Robert,Wu, Xiao-Feng,Xu, Jian-Xing,Yuan, Yang
(2020/07/21)

Nickel-catalyzed carboxylation of aryl iodides with lithium formate through catalytic CO recycling
A protocol for the Ni-catalyzed carboxylation of aryl iodides with formate has been developed with good functional group compatibility for the synthesis of a variety of aromatic carboxylic acids under mild conditions. The reaction tolerates other functionalities for cross-coupling, such as aryl bromide, aryl chloride, aryl tosylate, and aryl pinacol boronate. The reaction proceeds through a carbonylation process with in situ generated carbon monoxide in the presence of a catalytic amount of acetic anhydride and lithium formate, avoiding the use of gaseous CO. The strategy of CO recycling in catalytic amounts is critical for the success of the reaction.
Fu, Ming-Chen,Fu, Yao,Shang, Rui,Wu, Ya-Nan
supporting information
p. 4067 - 4069
(2020/04/20)

Ni-Catalyzed Carboxylation of C(sp2)-S Bonds with CO2: Evidence for the Multifaceted Role of Zn
Nickel-catalyzed reductive carboxylation reactions of aryl electrophiles typically require the use of metallic reducing agents. At present, the prevailing perception is that these serve as both a source of electrons and as a source of Lewis acids that may aid CO2 insertion into the Ni-C bond. Herein, we provide evidence for the in situ formation of organometallic species from the metallic reductant, a step that has either been ruled out or has been unexplored in catalytic carboxylation reactions with metal powder reductants. Specifically, we demonstrate that Zn(0) acts as a reductant and that Zn(II) generates arylzinc species that might play a role in the C(sp2)-S carboxylation of arylsulfonium salts. Overall, the reductive Ni-catalyzed C(sp2)-S carboxylation reaction proceeds under mild conditions in a non-amide solvent, displays a wide substrate scope, and can be applied to the formal para C-H carboxylation of arenes.
Yanagi, Tomoyuki,Somerville, Rosie J.,Nogi, Keisuke,Martin, Ruben,Yorimitsu, Hideki
p. 2117 - 2123
(2020/02/28)

Cobalt-Catalyzed Reductive Carboxylation of Aryl Bromides with Carbon Dioxide
Cobalt-catalyzed reductive carboxylation of aryl bromides with carbon dioxide has been developed. The reaction proceeded under one atm pressure of CO2 at 40 °C in the presence of cobalt iodide/2,2′-bipyridine catalysts and zinc dust as a reducing reagent. Various aryl bromides could be converted to the corresponding carboxylic acids in good to high yields. Preliminary mechanistic experiments ruled out intervention of intermediate organozinc species for carboxylation with CO2, thus suggesting a direct CO2 insertion into the corresponding ArCoBr species. (Figure presented.).
Hang, Wei,Yi, Yaping,Xi, Chanjuan
supporting information
p. 2337 - 2341
(2020/04/30)

Peptidomimetic plasmepsin inhibitors with potent anti-malarial activity and selectivity against cathepsin D
Following up the open initiative of anti-malarial drug discovery, a GlaxoSmithKline (GSK) phenotypic screening hit was developed to generate hydroxyethylamine based plasmepsin (Plm) inhibitors exhibiting growth inhibition of the malaria parasite Plasmodium falciparum at nanomolar concentrations. Lead optimization studies were performed with the aim of improving Plm inhibition selectivity versus the related human aspartic protease cathepsin D (Cat D). Optimization studies were performed using Plm IV as a readily accessible model protein, the inhibition of which correlates with anti-malarial activity. Guided by sequence alignment of Plms and Cat D, selectivity-inducing structural motifs were modified in the S3 and S4 sub-pocket occupying substituents of the hydroxyethylamine inhibitors. This resulted in potent anti-malarials with an up to 50-fold Plm IV/Cat D selectivity factor. More detailed investigation of the mechanism of action of the selected compounds revealed that they inhibit maturation of the P. falciparum subtilisin-like protease SUB1, and also inhibit parasite egress from erythrocytes. Our results indicate that the anti-malarial activity of the compounds is linked to inhibition of the SUB1 maturase plasmepsin subtype Plm X.
Zogota, Rimants,Kinena, Linda,Withers-Martinez, Chrislaine,Blackman, Michael J.,Bobrovs, Raitis,Pantelejevs, Teodors,Kanepe-Lapsa, Iveta,Ozola, Vita,Jaudzems, Kristaps,Suna, Edgars,Jirgensons, Aigars
supporting information
p. 344 - 352
(2018/12/11)

Nucleophilic oxidation and catalytic electrophilic reaction of copper alkyl peroxo complexes using temperature control
The present invention refers to temperature control using copper oxidation catalysts and electrophilic response relates to nucleophilic alkyl it ladles, the iodine complex, The present invention refers to low temperature conditions capable of inducing nucleophilic oxidation reaction while it ladles, the iodine complex alkyl copper, copper complex is added catalytic oxidation reaction capable of equal to or less than. (by machine translation)
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Paragraph 0111-0122; 0124-0129; 0138-0143

(2019/09/10)

Preparation method of substituted benzoic acid compounds
The invention relates to the field of production of chemical products, in particular to a preparation method of substituted benzoic acid compounds represented as general formula (II) in the description. The preparation method comprises steps as follows: corresponding substituted alkyl benzene represented as general formula (I) in the description is taken as a raw material, dilute nitric acid is taken as a reaction medium, oxygen is taken as an oxidant, an imide compound with a structure represented as formula (III) in the description or formula (IV) in the description is selected as a catalyst, all materials are subjected to catalytic oxidation in a high-pressure kettle, and substituted benzoic acid is prepared, wherein R1 is C1-C4 alkyl and R2 is halogen, nitryl, C1-C4 alkyl, methoxyl andtrifluoromethyl. The green preparation method of the substituted benzoic acid compounds is provided and has the advantages of high production purity, simple preparation, mild reaction conditions, simple aftertreatment, low cost and no pollution.
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Paragraph 0032; 0033

(2019/05/08)

Synthesis method of benzoic acid compounds
The invention discloses a photocatalytic oxidation synthesis method of benzoic acid compounds, and the photocatalytic oxidation synthesis method comprises the following specific steps: mixing and dissolving toluene compounds and a catalyst in a solvent, reacting for 24-60h in the presence of an oxidant under the conditions of 350-460 nm LED illumination and a temperature of 20-80 DEG C, and performing post-treatment on the reaction liquid to obtain the benzoic acid compounds. The photocatalytic oxidation synthesis method has the advantages of no need of metal catalysts, simple operation and mild reaction conditions; oxygen is used as an oxidant, and the photocatalytic oxidation synthesis method has high atom economy, cheap reagent and environmental protection. The photocatalytic oxidationsynthesis method has good substrate applicability, and various substituents can realize the synthesis of corresponding benzoic acid compounds.
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Paragraph 0162; 0163; 0164; 0165

(2019/12/25)

Two-Phase Reactions in Microdroplets
Improved two phase chemical reactions (liquid-liquid or liquid-gas) are provided by forming microdroplets of either or both liquid reagents and configuring the reaction as a collision between the microdroplet reagent and the other reagent. We have found that this approach can provide high reaction yields in short times (1 s) without the use of a phase transfer catalyst.
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Paragraph 0069; 0070; 0083; 0084

(2019/12/01)

Method for copper-catalyzed carboxylation reaction of arylboronic acid and carbon dioxide
The invention discloses a method for a copper-catalyzed carboxylation reaction of arylboronic acid and carbon dioxide. According to the method, carbon dioxide is used as a C1 source, copper catalysisis adopted, alkoxide serves as alkali, and a reaction is carried out in an organic solvent; the method is simple in process and easy to implement, and shows wide functional group compatibility; the method allows various arylboronic acids such as monosubstituted or polysubstituted phenylboronic acid, polycyclic aromatic hydrocarbon boronic acid and benzoheterocyclic boronic acid to be converted into corresponding arylcarboxylic acids with considerable yield under mild conditions; and the produced carboxylic acids have important application value, and can be used for deriving a great number of other common chemical substances, such as acyl halide, acid anhydride, ester and amide.
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Paragraph 0083; 0084

(2019/12/29)

Nickel-catalyzed carboxylation of aryl and heteroaryl fluorosulfates using carbon dioxide
The development of efficient and practical methods to construct carboxylic acids using CO2 as a C1 synthon is of great importance. Nickel-catalyzed carboxylation of aryl fluorosulfates and heteroaryl fluorosulfates with CO2 is described, affording arene carboxylic acids with good to excellent yields under mild conditions. In addition, a one-pot phenol fluorosulfation/carboxylation is developed.
Ma, Cong,Zhao, Chuan-Qi,Xu, Xue-Tao,Li, Zhao-Ming,Wang, Xiang-Yang,Zhang, Kun,Mei, Tian-Sheng
p. 2464 - 2467
(2019/04/10)

Palladium-Catalyzed Visible-Light-Driven Carboxylation of Aryl and Alkenyl Triflates by Using Photoredox Catalysts
A visible-light-driven carboxylation of aryl and alkenyl triflates with CO2 is developed by using a combination of Pd and photoredox catalysts. This reaction proceeds under mild conditions and can be applied to a wide range of substrates including acyclic alkenyl triflates.
Shimomaki, Katsuya,Nakajima, Tomoya,Caner, Joaquim,Toriumi, Naoyuki,Iwasawa, Nobuharu
supporting information
p. 4486 - 4489
(2019/06/24)

Efficient catalytic oxidation of methyl aromatic hydrocarbon with: N -alkyl pyridinium salts
A series of N-alkyl pyridinium salts were synthesized and employed as metal-free catalyst for the selective oxidation of methyl aromatic hydrocarbon with molecular oxygen. The electronic effect of the substitutes was found to be an important factor for the catalytic performance. With the introduction of electron-donating substitute -N(CH3)2, the conversion of p-xylene and selectivity of p-toluic acid could be simultaneously increased. 1-Benzyl-4-N,N-dimethylaminopyridinium salt showed the highest catalytic activity, and 95% conversion with 84% of selectivity to p-toluic acid could be obtained for the selective oxidation of p-xylene. Several methyl aromatic hydrocarbons could all be efficiently oxidized with the reported catalyst at the absence of any metal species.
Zhang, Qiaohong,He, Honghao,Wang, Huibin,Zhang, Zhan,Chen, Chen
p. 38891 - 38896
(2019/12/11)

Continuous Platform to Generate Nitroalkanes On-Demand (in Situ) Using Peracetic Acid-Mediated Oxidation in a PFA Pipes-in-Series Reactor
The synthetic utility of the aza-Henry reaction can be diminished on scale by potential hazards associated with the use of peracid to prepare nitroalkane substrates and the nitroalkanes themselves. In response, a continuous and scalable chemistry platform to prepare aliphatic nitroalkanes on-demand using the oxidation of oximes with peracetic acid and direct reaction of the nitroalkane intermediate in an aza-Henry reaction is reported. A uniquely designed pipes-in-series plug-flow tube reactor addresses a range of process challenges, including stability and safe handling of peroxides and nitroalkanes. The subsequent continuous extraction generates a solution of purified nitroalkane, which can be directly used in the following enantioselective aza-Henry chemistry to furnish valuable chiral diamine precursors with high selectivity, thus completely avoiding isolation of the potentially unsafe low-molecular-weight nitroalkane intermediate. A continuous campaign (16 h) established that these conditions were effective in processing 100 g of the oxime and furnishing 1.4 L of nitroalkane solution.
Tsukanov, Sergey V.,Johnson, Martin D.,May, Scott A.,Kolis, Stanley P.,Yates, Matthew H.,Johnston, Jeffrey N.
supporting information
p. 971 - 977
(2018/08/28)

Bis(methoxypropyl) ether-promoted oxidation of aromatic alcohols into aromatic carboxylic acids and aromatic ketones with O2 under metal- and base-free conditions
We describe an eco-friendly, practical and operationally simple procedure for the bis(methoxypropyl) ether-promoted oxidation of aromatic alcohols into aromatic carboxylic acids and aromatic ketones with atmospheric dioxygen as the sole oxidant. This chemical process is clean with high conversion and good selectivity, and an external initiator, catalyst, additive and base are not required. The virtue of this reaction is highlighted by its easily available and economical raw materials and excellent functional group tolerance (acid-, base- and oxidant-labile groups).
Liu, Kai-Jian,Jiang, Si,Lu, Ling-Hui,Tang, Ling-Li,Tang, Shan-Shan,Tang, Hai-Shan,Tang, Zilong,He, Wei-Min,Xu, Xinhua
supporting information
p. 3038 - 3043
(2018/07/13)

Silver(I)-Catalyzed Widely Applicable Aerobic 1,2-Diol Oxidative Cleavage
The oxidative cleavage of 1,2-diols is a fundamental organic transformation. The stoichiometric oxidants that are still predominantly used for such oxidative cleavage, such as H5IO6, Pb(OAc)4, and KMnO4, generate stoichiometric hazardous waste. Herein, we describe a widely applicable and highly selective silver(I)-catalyzed oxidative cleavage of 1,2-diols that consumes atmospheric oxygen as the sole oxidant, thus serving as a potentially greener alternative to the classical transformations.
Zhou, Zhong-Zhen,Liu, Mingxin,Lv, Leiyang,Li, Chao-Jun
p. 2616 - 2620
(2018/02/13)

Cobalt/N-Hydroxyphthalimide(NHPI)-Catalyzed Aerobic Oxidation of Hydrocarbons with Ionic Liquid Additive
A highly efficient and solvent-free system of cobalt/NHPI-catalyzed aerobic oxidation of hydrocarbons was developed using imidazolium-based ionic liquid (IL) as an additive. These amphipathic ILs were found self-assemble at the interface between the organic hydrocarbons and the aqueous phase of catalyst combination (Co/NHPI), with forming a solution of reversed multilamellar vesicles for catalysis. The initial reaction rate was influenced by both the composition of microdomains and the structure of IL launched. Consequently, a proper water content (χH2O) of wet IL was requisite to reach the optimum reactivity. Besides, the interfacial boundary between aqueous and organic phase composed by C2-alkylated imidazolium ILs, such as [bdmim]SbF6 and [C12dmim]SbF6, not only has ternary aggregates (hydrocarbons/IL/H2O) of higher stability but renders O2 a faster diffusion rate and higher concentration, thereby offering a high reactivity of the protocol towards hydrocarbon oxidation.
Mahmood, Sajid,Xu, Bao-Hua,Ren, Tian-Lu,Zhang, Zhi-Bo,Liu, Xiao-Min,Zhang, Suo-Jiang
p. 90 - 96
(2018/02/13)

Preparative microdroplet synthesis of carboxylic acids from aerobic oxidation of aldehydes
Single liquid-phase and liquid-liquid phase reactions in microdroplets have shown much faster kinetics than that in the bulk phase. This work extends the scope of microdroplet reactions to gas-liquid reactions and achieves preparative synthesis. We report highly efficient aerobic oxidation of aldehydes to carboxylic acids in microdroplets. Molecular oxygen plays two roles: (1) as the sheath gas to shear the aldehyde solution into microdroplets, and (2) as the sole oxidant. The dramatic increase of the surface-area-to-volume ratio of microdroplets compared to bulk solution, and the efficient mixing of gas and liquid phases using spray nozzles allow effective mass transfer between aldehydes and molecular oxygen. The addition of catalytic nickel(ii) acetate is shown to accelerate further microdroplet reactions of this kind. We show that aliphatic, aromatic, and heterocyclic aldehydes can be oxidized to the corresponding carboxylic acids in a mixture of water and ethanol using the nickel(ii) acetate catalyst, in moderate to excellent yields (62-91%). The microdroplet synthesis is scaled up to make it preparative. For example, aerobic oxidation of 4-tert-butylbenzaldehyde to 4-tert-butylbenzoic acid was achieved at a rate of 10.5 mg min-1 with an isolated product yield of 66%.
Yan, Xin,Lai, Yin-Hung,Zare, Richard N.
p. 5207 - 5211
(2018/06/21)

Method for preparing aryl formic acid by adopting aryl alkyl ketone as raw material
The invention discloses a method for preparing aryl formic acid by adopting aryl alkyl ketone as a raw material. The method is characterized in that: aryl alkyl ketone is used as a reaction substrate,iodine and Fe(NO3)3.9H2O are used catalysts to react for 8 to 16 hours in dimethyl sulfoxide at the temperature 110 to 140 DEG C in an oxygen atmosphere of one barometric pressure, and after the reaction is ended, the reactant is separated to obtain the aryl formic acid. According to the synthetic method of the invention, the environment-friendly iron catalyst is used; the environment-friendly green oxidant oxygen is used; the reaction is performed at the normal pressure, and no pressurizing device is needed; and the application range of the reaction substrate is wide.
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Paragraph 0055; 0056

(2019/01/08)

Catalytic oxidation synthesis method of aryl formic acid
The invention discloses a catalytic oxidation synthesis method of aryl formic acid. According to the method, aryl alkyl ketone is used as a reaction substrate, iodine is used as a catalyst, and dimethyl sulfoxide (DMSO) is taken as an oxidizing agent; the method comprises the steps of adding the reaction substrate into chlorobenzene, and carrying out a reaction for 2-4h at the temperature of 110-135 DEG C; after that, cooling reaction liquid to the room temperature, adding another oxidizing agent, i.e., t-butylhydroperoxide (TBHP), continuously carrying out a reaction at the temperature of 110-135 DEG C, and separating after the reaction is finished so as to obtain the aryl formic acid. The method provided by the invention avoids the use of a transition metal catalyst, thus reducing the consumption of toxic and harmful additives; the reaction substrate is wide in application scope.
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Paragraph 0054; 0055

(2018/07/30)

Oxidative C-C Bond Cleavage for the Synthesis of Aryl Carboxylic Acids from Aryl Alkyl Ketones
A metal-free and one-pot two-step synthesis of aryl carboxylic acids from aryl alkyl ketones has been achieved. The reactions were performed with iodine as the catalyst, DMSO and TBHP as the oxidants. Under the optimal reaction conditions, a number of aryl alkyl ketones could be converted into their corresponding aryl carboxylic acids in good to excellent yields (up to 94%).
Xu, Liang,Wang, Shengpeng,Chen, Bajin,Li, Meichao,Hu, Xinquan,Hu, Baoxiang,Jin, Liqun,Sun, Nan,Shen, Zhenlu
p. 1505 - 1509
(2018/05/25)

I2/Fe(NO3)3·9H2O-catalyzed oxidative synthesis of aryl carboxylic acids from aryl alkyl ketones and secondary benzylic alcohols
An interesting and convenient procedure for the oxidative transformation of aryl alkyl ketones and secondary benzylic alcohols to aryl carboxylic acids has been developed. By using iodine and Fe(NO3)3·9H2O as the catalysts, DMSO and oxygen as the oxidants, the desired aryl carboxylic acids were synthesized in moderate to excellent yields (up to 91%).
Xu, Liang,Chen, Yingying,Shen, Zhenlu,Wang, Yuru,Li, Meichao
supporting information
p. 4349 - 4354
(2018/11/03)

Tert-Butyl Nitrite-Mediated Synthesis of N-Nitrosoamides, Carboxylic Acids, Benzocoumarins, and Isocoumarins from Amides
This work reports tert-butyl nitrite (TBN) as a multitask reagent for (1) the controlled synthesis of N-nitrosoamide from N-alkyl amides, (2) hydrolysis of N-methoxyamides to carboxylic acids, (3) metal- and oxidant-free benzocoumarin synthesis from ortho-aryl-N-methoxyamides via N-H, C-N, and C-H bond activation, and (4) isocoumarin synthesis using Ru(II)/PEG as a recyclable catalytic system via ortho-C-H activation and TBN as an oxygen source. The sequential functional group interconversion of amide to acid has also been examined using IR spectroscopic analysis. Additionally, this methodology is highly advantageous due to short reaction time, gram scale synthesis, and broad substrate scope.
Yedage, Subhash L.,Bhanage, Bhalchandra M.
p. 5769 - 5781
(2017/06/07)

Transition-Metal- and Halogen-Free Oxidation of Benzylic sp 3 C-H Bonds to Carbonyl Groups Using Potassium Persulfate
Aryl carbonyl compounds including acetophenones, benzophenones, imides, and benzoic acids are prepared from benzyl substrates using potassium persulfate as oxidant with catalytic pyridine in acetonitrile under mild conditions. Neither transition metals nor halogens are involved in the reactions.
Hu, Yixin,Zhou, Lihong,Lu, Wenjun
supporting information
p. 4007 - 4016
(2017/08/29)

A arab League Fu Benzong synthetic method
The invention discloses a synthetic method of avobenzone. The avobenzone is prepared by subjecting phenetole and methylbenzene, as starting materials, to alkylation, oxidation, esterification, acylation and condensation reaction. During oxidation, the oxidant potassium permanganate is added to a reaction system six times, thus thermal decomposition and deacidification of the potassium permanganate is avoided, and reaction yield is higher. During esterification, with methylsulphonic acid as catalyst, P-tert-butyl benzoic acid and methanol are subjected to reflux reaction for 8 hours according to a molar ratio: 1:7; the methanol is added in two stages for reaction, and the problem that water diversion fails in the reaction process is solved. During acylation, phosphotungstic acid is used as catalyst, reaction selectivity is improved, post-reaction treatment is simpler, and reaction yield is higher; the phosphotungstic acid is recyclable, thus cost is saved and industrial production is more benefited.
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Paragraph 0018; 0025; 0032

(2017/07/04)

Harnessing the Reactivity of Iridium Hydrides by Air: Iridium-Catalyzed Oxidation of Aldehydes to Acids in Water
An iridium-catalyzed oxidation of aldehydes to acids was realized by using air as the oxidant and water as the solvent in the presence of base. Interestingly, the same type of catalysts were also used for the reduction of aldehydes under acidic conditions. A common iridium hydride intermediate is proposed for both redox reactions. The oxidation has a number of advantages such as high yields, great functionality tolerance, and easy purification without chromatography.
Yang, Zhanhui,Luo, Renshi,Zhu, Zhongpeng,Yang, Xuerong,Tang, Weiping
supporting information
p. 4095 - 4098
(2017/11/21)