- Integrating Hydrogen Production and Transfer Hydrogenation with Selenite Promoted Electrooxidation of α-Nitrotoluenes to E-Nitroethenes
-
Developing an electrochemical carbon-added reaction with accelerated kinetics to replace the low-value and sluggish oxygen evolution reaction (OER) is markedly significant to pure hydrogen production. Regulating the critical steps to precisely design electrode materials to selectively synthesize targeted compounds is highly desirable. Here, inspired by the surfaced adsorbed SeOx2? promoting OER, NiSe is demonstrated to be an efficient anode enabling α-nitrotoluene electrooxidation to E-nitroethene with up to 99 % E selectivity, 89 % Faradaic efficiency, and the reaction rate of 0.25 mmol cm?2 h?1 via inhibiting side reactions for energy-saving hydrogen generation. The high performance can be associated with its in situ formed NiOOH surface layer and absorbed SeOx2? via Se leaching-oxidation during electrooxidation, and the preferential adsorption of two -NO2 groups of intermediate on NiOOH. A self-coupling of α-carbon radicals and subsequent elimination of a nitrite molecule pathway is proposed. Wide substrate scope, scale-up synthesis of E-nitroethene, and paired productions of E-nitroethene and hydrogen or N-protected aminoarenes over a bifunctional NiSe electrode highlight the promising potential. Gold also displays a similar promoting effect for α-nitrotoluene transformation like SeOx2?, rationalizing the strategy of designing materials to suppress side reactions.
- Chong, Xiaodan,Liu, Cuibo,Wang, Changhong,Yang, Rong,Zhang, Bin
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supporting information
p. 22010 - 22016
(2021/09/02)
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- Synthesis of highly potent anti-inflammatory compounds (ROS inhibitors) from isonicotinic acid
-
In search of anti-inflammatory compounds, novel scaffolds containing isonicotinoyl motif were synthesized via an efficient strategy. The compounds were screened for their in vitro antiinflammatory activity. Remarkably high activities were observed for isonicotinates 5-6 and 8a-8b. The compound 5 exhibits an exceptional IC50 value (1.42 ± 0.1 μg/mL) with 95.9% inhibition at 25 μg/mL, which is eight folds better than the standard drug ibuprofen (11.2 ± 1.9 μg/mL). To gain an insight into the mode of action of anti-inflammatory compounds, molecular docking studies were also performed. Decisively, further development and fine tuning of these isonicotinates based scaffolds for the treatment of various aberrations is still a wide-open field of research.
- Yaqoob, Sana,Nasim, Nourina,Khanam, Rahila,Wang, Yan,Jabeen, Almas,Qureshi, Urooj,Ul-Haq, Zaheer,El-Seedi, Hesham R.,Jiang, Zi-Hua,Khan, Farooq-Ahmad
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- Salicylaldehyde Schiff base derivative based on ureido pyrimidone, and supramolecular polymer
-
The invention relates to a salicylaldehyde Schiff base derivative and a supramolecular polymer, and particularly discloses a salicylaldehyde Schiff base derivative based on ureido pyrimidone, and a supramolecular polymer formed by orthogonally self-assemb
- -
-
Paragraph 0053-0057
(2021/08/11)
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- Ultrasound promoted environmentally benign, highly efficient, and chemoselective N-tert-butyloxycarbonylation of amines by reusable sulfated polyborate
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The sulfated polyborate catalyzed an efficient and chemoselective N-tert-butyloxycarbonylation of amines under ultrasonic irradiation is developed. A broad substrate scope has been demonstrated for N-Boc protection of various primary/secondary amines. It allows converting several aliphatic/aryl/heteroaryl amines, amino alcohol, aminoester, and chiral amines to their N-Boc-protected derivatives under solvent-free conditions with excellent yields. The protocol has several advantages such as easy catalyst, and product isolation, short reaction time, excellent yields, outstanding chemoselectivity, and catalyst recyclability, among others. This makes the process practicable, economical, and environmentally benign.
- Pise, Ashok S.,Ingale, Ajit P.,Dalvi, Navnath R.
-
supporting information
p. 3768 - 3780
(2021/10/26)
-
- Thiamine hydrochloride as a recyclable organocatalyst for the efficient and chemoselective N-tert-butyloxycarbonylation of amines
-
Thiamin hydrochloride promoted highly efficient and ecofriendly approach has been described for the chemoselective N-tert-butyloxycarbonylation of amines under solvent-free conditions at ambient temperature. The demonstrated approach has been applicable for the N-Boc protection of variety of aliphatic, aryl, heteroaryl amines. The chemoselective protection of amino group occurs in chiral amines and amino alcohol without racemization in high yield. Thiamin hydrochloride is stable, economical, easy to handle and environmentally friendly.
- Ingale, Ajit P.,Garad, Dnyaneshwar N.,Ukale, Dattatraya,Thorat, Nitin M.,Shinde, Sandeep V.
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supporting information
p. 3791 - 3804
(2021/11/04)
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- Sulfated tungstate: A highly efficient, recyclable and ecofriendly catalyst for chemoselective N-tert butyloxycarbonylation of amines under the solvent-free conditions
-
Sulfated tungstate catalyzed an efficient and ecofriendly protocol has been described for the chemoselective N-tert-butyloxycarbonylation of amines under the solvent-free conditions at room temperature. The variety of functionalized aliphatic, aromatic and heteroaromatic amines efficiently undergoes the N-tert-butyloxycarbonylation under the developed protocol. The aminoalcohol, aminophenol, aminoester as well as various chiral amines underwent the chemoselective N-Boc protection under the optimized reaction condition. The rapid reaction rate, mild conditions, very good functional group tolerance, excellent yield, solvent-free, easy recovery products and excellent catalyst recyclability are the advantages of this protocol. This makes the protocol feasible, economical and environmentally benign.
- Ingale, Ajit P.,Shinde, Sandeep V.,Thorat, Nitin M.
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supporting information
p. 2528 - 2543
(2021/07/02)
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- Nanoceria as an efficient and green catalyst for the chemoselective N-tert-butyloxycarbonylation of amines under the solvent-free conditions
-
Nanocerium oxide mediated an efficient and green protocol has been described for the chemoselective N-tert-butyloxycarbonylation of amines under the solvent-free conditions at ambient temperature. Various aliphatic, aromatic and heteroaromatic amines were protected using developed protocol and several functional groups such as alcohol, phenol and ester were well tolerated under these conditions. The rapid reaction rate, mild conditions, very good functional group tolerance, excellent yield, solvent-free, easy recovery products and excellent catalyst recyclability are the advantages of this protocol. This makes the protocol feasible, economical and environmentally benign.
- Garad, Dnyaneshwar N.,Ingale, Ajit P.,Shinde, Sandeep V.,Ukale, Dattatraya
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supporting information
p. 1656 - 1668
(2021/04/05)
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- Smart supramolecular nanofibers and nanoribbons from uniform amphiphilic azobenzene oligomers
-
A series of self-assembled 1D nanostructures, including straight and helix nanofibers, nanoribbons, and nanobelts, were fabricated from uniform amphiphilic azobenzene oligomers with tunable molecular weight and side chain functionality, promoted by multiple and cooperative supramolecular interactions. Additionally, the morphological transformation of the nanofibers was achieved during the photoisomerization process.
- Li, Lishan,Zhang, Jiandong,Liu, Min,Shi, Xianheng,Zhang, Wei,Li, Yiwen,Zhou, Nianchen,Zhang, Zhengbiao,Zhu, Xiulin
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supporting information
p. 2192 - 2195
(2021/03/06)
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- Selective hydroboration of equilibrating allylic azides
-
The iridium(i)-catalyzed hydroboration of equilibrating allylic azides is reported to provide only the anti-Markovnikov product of alk-1-ene isomers in good yields and with good functional group tolerance.
- Liu, Ruzhang,Xu, Jun,Zhang, Yuanyuan
-
supporting information
p. 8913 - 8916
(2021/09/13)
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- POLYAROMATIC UREA DERIVATIVES AND THEIR USE IN THE TREATMENT OF MUSCLE DISEASES
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The current invention provides urea derivatives, in particular compounds having the core structure heteroaryl-NH-CO-NH-aryl-O- heteroaryl, for use in treating, ameliorating, delaying, curing and/ or preventing a disease or condition associated with muscle cells and/or satellite cells, such as Duchenne muscular dystrophy, Becker muscular dystrophy, cachexia or sarcopenia.
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Page/Page column 126
(2021/01/29)
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- Danshensu derivativeS as well as preparation method and medical application thereof
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The invention discloses Danshensu derivatives as well as a preparation method and medical application thereof. The derivatives have a general structure as shown in a general formula (I) shown in the specification, wherein R1 represents OH or OCH3; R2 represents H or Ac; and R3 represents a first structure, a second structure or a third structure shown in the specification. Compared with a raw material medicine, the derivatives synthesized by the invention have the advantages that the fat solubility is increased, so that the derivatives can penetrate through the blood-brain barrier (BBB), the medicine stability is greatly improved, and the curative effect is further improved. Therefore, the derivatives disclosed by the invention can be applied to preparation of drugs for preventing, treating, treating and/or reducing the cerebral infarction volume of a patient, improving the balance coordination ability of the patient and other diseases, and a new therapeutic drug is provided for preventing and treating cerebrovascular or cranial nerve diseases.
- -
-
Paragraph 0077-0079; 0090
(2021/09/04)
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- Oxygen bridge bicyclo - [2.2.1] - heptene compounds containing different covalent bullet structures, and preparation and application thereof
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The invention discloses an oxygen bridge bicyclo - [2.2.1] - heptene compound containing different covalent popping structures as well as preparation and application thereof, and belongs to the technical field of targeted drugs. As shown in general formula (I) or general formula (II), furan derivatives and vinylsulfonamide derivatives or vinylsulfonate derivatives containing different covalent popping heads are prepared by reacting Diels-Alder to obtain a compound of the present invention. The compound can be used for preparing anti-breast cancer drugs. A medicament for the degradation of estrogen receptors, a medicament for a mutant estrogen receptor. Compared with the existing anti-breast cancer drug tamoxifen, MCF-7 cells have stronger inhibitory activity and have the ability to down-regulate the estrogen receptor level, and the activity shown for the mutant estrogen receptor is 4 - times of 5-10 hydroxytamoxifen.
- -
-
Paragraph 0132-0133
(2021/11/03)
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- Iron-catalyzed arene C-H hydroxylation
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The sustainable, undirected, and selective catalytic hydroxylation of arenes remains an ongoing research challenge because of the relative inertness of aryl carbon-hydrogen bonds, the higher reactivity of the phenolic products leading to over-oxidized by-products, and the frequently insufficient regioselectivity. We report that iron coordinated by a bioinspired L-cystine-derived ligand can catalyze undirected arene carbon-hydrogen hydroxylation with hydrogen peroxide as the terminal oxidant. The reaction is distinguished by its broad substrate scope, excellent selectivity, and good yields, and it showcases compatibility with oxidation-sensitive functional groups, such as alcohols, polyphenols, aldehydes, and even a boronic acid. This method is well suited for the synthesis of polyphenols through multiple carbon-hydrogen hydroxylations, as well as the late-stage functionalization of natural products and drug molecules.
- Cheng, Lu,Wang, Huihui,Cai, Hengrui,Zhang, Jie,Gong, Xu,Han, Wei
-
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- Evaluation of 2-(piperidine-1-yl)-ethyl (PIP) as a protecting group for phenols: Stability to ortho-lithiation conditions and boiling concentrated hydrobromic acid, orthogonality with most common protecting group classes, and deprotection via Cope elimination or by mild Lewis acids
-
A new protecting group, 2-(piperidine-1-yl)-ethyl (PIP), was evaluated as a protecting group for phenols. The PIP group was stable to ortho-lithiation conditions and refluxing with concentrated hydrobromic acid. Deprotection was accomplished by two routes, oxidation to N-oxides followed by Cope elimination (CE) and subsequent hydrolysis or ozonolysis of the vinyl ether or one-step deprotection by BBr3?Me2S. The PIP group is orthogonal to the O-benzyl, O-acetyl, O-t-butyldiphenylsilyl, O-methyl, O-p-methoxybenzyl, O-allyl, O-tetrahydropyranyl and N-t-butoxy carbonyl groups. The CE step was systematically studied and was found to give higher yields when the reaction was performed in the presence of silylating agents.
- Norén, Rolf
-
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- Highly efficient chemoselective N-tert butoxycarbonylation of aliphatic/aromatic/heterocyclic amines using diphenylglycoluril as organocatalyst
-
An efficient approach for the Chemoselective N-tert-butoxycarbonylation of a variety of amines using diphenylglycoluril as organocatalyst has been described. For the first time, a plausible mechanism for the N-tert-butoxycarbonylation has been proposed using density functional theory (DFT) calculations supported by NMR studies. The reusability of the organocatalyst and observation of the desired N-Boc protected amines being formed without the formation of side products like urea, oxazolidinone, isocyanate, and N, N-di-Boc derivatives makes the present protocol desirable.
- Awasthi, Amardeep,Mukherjee, Anagh,Singh, Mandeep,Rathee, Garima,Vanka, Kumar,Chandra, Ramesh
-
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- Divinylsulfonamides enable the construction of homogeneous antibody–drug conjugates
-
Methods that site-specifically attach payloads to an antibody with controlled DAR (Drug-Antibody Ratio) are highly desirable for the generation of homogeneous antibody-drug conjugates (ADCs). We describe the use of N-phenyl-divinylsulfonamide scaffold as
- Huang, Rong,Sheng, Yao,Wei, Ding,Lu, Wenwen,Xu, Zili,Chen, Hongli,Jiang, Biao
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- A Greener Approach for the Chemoselective Boc Protection of Amines Using Sulfonated Reduced Graphene Oxide as a Catalyst in Metal- And Solvent-Free Conditions
-
Sulfonated reduced graphene oxide (SrGO) has displayed great potential as a solid acid catalyst due to its efficiency, cost-effectiveness, and reliability. In this study, SrGO was synthesized by the introduction of sulfonic acid-containing aryl radicals onto chemically reduced graphene oxide using ultrasonication. The SrGO catalyst was characterized by Fourier Transform Infrared (FTIR) spectroscopy, Raman spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and transmission electron microscopy (TEM). Further, SrGO was effectively utilized as a metal-free and reusable solid acid catalyst for the chemoselective N - t -Boc protection of various aromatic and aliphatic amines under solvent-free conditions. The N - t -Boc protection of amines was easily achieved under ambient conditions affording high yields (84-95percent) in very short reaction times (5 min-2 h). The authenticity of the approach was confirmed by a crystal structure. The catalyst could be easily recovered and was reused up to seven consecutive catalytic cycles without any substantial loss in its activity.
- Awasthi, Satish K.,Mishra, Anupam,Mittal, Rupali
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p. 591 - 601
(2020/02/13)
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- Chemoselective and Site-Selective Lysine-Directed Lysine Modification Enables Single-Site Labeling of Native Proteins
-
The necessity for precision labeling of proteins emerged during the efforts to understand and regulate their structure and function. It demands selective attachment of tags such as affinity probes, fluorophores, and potent cytotoxins. Here, we report a method that enables single-site labeling of a high-frequency Lys residue in the native proteins. At first, the enabling reagent forms stabilized imines with multiple solvent-accessible Lys residues chemoselectively. These linchpins create the opportunity to regulate the position of a second Lys-selective electrophile connected by a spacer. Consequently, it enables the irreversible single-site labeling of a Lys residue independent of its place in the reactivity order. The user-friendly protocol involves a series of steps to deconvolute and address chemoselectivity, site-selectivity, and modularity. Also, it delivers ordered immobilization and analytically pure probe-tagged proteins. Besides, the methodology provides access to antibody-drug conjugate (ADC), which exhibits highly selective anti-proliferative activity towards HER-2 expressing SKBR-3 breast cancer cells.
- Adusumalli, Srinivasa Rao,Kalra, Neetu,Purushottam, Landa,Rai, Vishal,Rawale, Dattatraya Gautam,Reddy, Neelesh C.,Shukla, Sanjeev,Thakur, Kalyani
-
supporting information
p. 10332 - 10336
(2020/04/27)
-
- Bioisosteric Replacement of Amide Group with 1,2,3-Triazoles in Acetaminophen Addresses Reactive Oxygen Species-Mediated Hepatotoxic Insult in Wistar Albino Rats
-
Acetaminophen (AP) is a popularly recommended over-the-counter analgesic-antipyretic in clinical use. However, the drug is handicapped by the occurrence of hepatotoxic insult following acute ingestion. Consequently, AP-induced hepatotoxicity is often impl
- Agrawal, Ramkishore,Das, Debashree,Gajbhiye, Asmita,Mishra, Shweta,Sahu, Adarsh,Sahu, Preeti,Sakthivel, Ayyamperumal
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-
- A scalable and green one-minute synthesis of substituted phenols
-
A mild, green and highly efficient protocol was developed for the synthesis of substituted phenols via ipso-hydroxylation of arylboronic acids in ethanol. The method utilizes the combination of aqueous hydrogen peroxide as the oxidant and H2O2/HBr as the reagent under unprecedentedly simple and convenient conditions. A wide range of arylboronic acids were smoothly transformed into substituted phenols in very good to excellent yields without chromatographic purification. The reaction is scalable up to at least 5 grams at room temperature with one-minute reaction time and can be combined in a one-pot sequence with bromination and Pd-catalyzed cross-coupling to generate more diverse, highly substituted phenols.
- Elumalai, Vijayaragavan,Hansen, J?rn H.
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p. 40582 - 40587
(2020/11/18)
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- Quantum Dot-Catalyzed Photoreductive Removal of Sulfonyl-Based Protecting Groups
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This Communication describes the use of CuInS2/ZnS quantum dots (QDs) as photocatalysts for the reductive deprotection of aryl sulfonyl-protected phenols. For a series of aryl sulfonates with electron-withdrawing substituents, the rate of deprotection for the corresponding phenyl aryl sulfonates increases with decreasing electrochemical potential for the two electron transfers within the catalytic cycle. The rate of deprotection for a substrate that contains a carboxylic acid, a known QD-binding group, is accelerated by more than a factor of ten from that expected from the electrochemical potential for the transformation, a result that suggests that formation of metastable electron donor–acceptor complexes provides a significant kinetic advantage. This deprotection method does not perturb the common NHBoc or toluenesulfonyl protecting groups and, as demonstrated with an estrone substrate, does not perturb proximate ketones, which are generally vulnerable to many chemical reduction methods used for this class of reactions.
- Perez, Kaitlyn A.,Rogers, Cameron R.,Weiss, Emily A.
-
supporting information
p. 14091 - 14095
(2020/06/08)
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- Anchimerically Assisted Selective Cleavage of Acid-Labile Aryl Alkyl Ethers by Aluminum Triiodide and N, N-Dimethylformamide Dimethyl Acetal
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Aluminum triiodide is harnessed by N,N-dimethylformamide dimethyl acetal (DMF-DMA) for the selective cleavage of ethers via neighboring group participation. Various acid-labile functional groups, including carboxylate, allyl, tert-butyldimethylsilyl (TBS), and tert-butoxycarbonyl (Boc), suffer the conditions intact. The method offers an efficient approach to cleaving catechol monoalkyl ethers and to uncovering phenols from acetal-type protecting groups such as methoxymethyl (MOM), methoxyethoxymethyl (MEM), and tetrahydropyranyl (THP) chemoselectively.
- Sang, Dayong,Yue, Huaxin,Zhao, Zhengdong,Yang, Pengtao,Tian, Juan
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p. 6429 - 6440
(2020/07/14)
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- Selective ether bond breaking method of aryl alkyl ether
-
The invention discloses a selective aryl alkyl ether cracking method, which comprises that aryl alkyl ether, aluminum iodide and an additive are subjected to a selective ether bond cleavage reaction in an organic solvent at a temperature of -20 DEG C to a reflux temperature to generate phenol and derivatives thereof. The method is mild in condition and simple and convenient to operate, is suitablefor cracking aryl alkyl ether containing o-hydroxyl and o-carbonyl and acetal ether, and can also be used for removing tertiary carbon hydroxyl protecting groups with higher steric hindrance, such astriphenylmethyl, tertiary butyl and the like.
- -
-
Paragraph 0258-0262
(2020/09/16)
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- Tert-Butyl(3-cyano-4,6-dimethylpyridin-2-yl)carbonate as a green and chemoselective N-tert-butoxycarbonylation reagent
-
The use of tert-butyl(3-cyano-4,6-dimethylpyridin-2-yl)carbonate as a chemoselective tert-butoxycarbonylation reagent for aromatic and aliphatic amines has been demonstrated. To gain insight into this reaction, in situ React IR technology was used to confirm the effectivity and chemoselectivity of this novel Boc reagent. The reaction was carried out chemoselectively in high yield under mild, environment-friendly conditions and was completed quickly within 1 hour. Simultaneously, the Boc carrier was easily recyclable, and has great application prospects for industrial production.
- Du, Fangyu,Zhou, Qifan,Fu, Yang,Zhao, Hanqi,Chen, Yuanguang,Chen, Guoliang
-
supporting information
p. 6549 - 6554
(2019/05/04)
-
- Antibody-medicine conjugate targeting EGFR and preparation method and application thereof
-
The invention relates to an antibody-medicine conjugate targeting an EGFR. The antibody-medicine conjugate targeting the EGFR is characterized in that the antibody-medicine conjugate of a structure shown in a formula I or pharmaceutically-accepted salt or solvate is involved. According to a structural formula of the antibody-medicine conjugate targeting the EGFR, n represents the medicine-antibody proportion and is 3-5; R is O or CONH or NHCO; R is in para-position or meta-position; p is 1-6; m is 0-20. According to the antibody-medicine conjugate targeting the EGFR, based on a bis-ethylene sulfamide connection connexin technology, the antibody-medicine conjugate targeting the EGFR is synthesized for the first time. According to the antibody-medicine conjugate targeting the EGFR, internal sulphur-sulphur bonds of an antibody are broken and then bridged, the conjugate with good uniformity and DAR of about 4 can be obtained, and the antibody is wide in application range.
- -
-
Paragraph 0079-0083
(2019/10/05)
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- Self-assembly of M4L4 tetrahedral cages incorporating pendant PS and PSe functionalised ligands
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Herein, the synthesis of metal-organic tetrahedral cages featuring flexible thio- and selenophosphate-based ligands is described. The cages were prepared by sub-component self-assembly of AP(OC6H4NH2-4)3 (A = S, Se) or SP(SC6H4NH2-4)3, 2-pyridinecarboxaldehyde, and either Fe[BF4]2 or Co[BF4]2. Preliminary host-guest studies into the ability of the pendant PS and PSe groups to interact with suitable substrates will be discussed.
- Butler, Patrick W. V.,Kruger, Paul E.,Ward, Jas S.
-
supporting information
p. 10304 - 10307
(2019/09/03)
-
- Indole compound as well as preparation method, pharmaceutical composition and application thereof
-
The invention discloses an indole compound as well as a preparation method, a pharmaceutical composition and an application thereof. Specifically, the invention relates to an indole derivative as shown in a general formula I and a medicinal salt thereof, a preparation method of the indole derivative, a composition containing one or more compounds, and applications of the compounds in preparation of medicines for preventing and/or treating diseases related to IDO1 and/or TDO.
- -
-
Paragraph 1210-1215
(2019/12/02)
-
- Quinoline or quinazoline compound as well as preparation method and application thereof
-
The invention relates to quinoline or quinazoline compound as well as a preparation process and application thereof. The structural formula is shown in the description. The quinoline or quinazoline compound can inhibit the activity of PFKFB3 in tumor cells, effectively block activation of key enzymes during a glycolysis process, and inhibit energy supply for tumor cells.
- -
-
Paragraph 0055; 0165; 0166
(2019/01/23)
-
- Copper-Catalyzed 1,2-Bistrifluoromethylation of Terminal Alkenes
-
Many efficient catalytic methods for the introduction of trifluoromethyl group (CF3) have been reported. Among them, the addition of CF3 and other components to alkenes is well known, and many components such as azides, cyanides, amines, and halides have been inserted into alkenes with CF3. However, to date the double catalytic insertion of CF3 into an alkene is unknown. Herein, we report the catalytic 1,2-bistrifluoromethylations of alkenes catalyzed by Copper (Cu). We used two CF3 sources, namely Umemoto's reagent and (trifluoromethyl)trimethylsilane (TMSCF3). Each reagent plays a unique role during this transformation; Umemoto's reagent generates CF3 radicals, while TMSCF3 is used to form CF3 anions. Copper (I) bromide (CuBr) exhibited the best catalytic activity for this reaction. We believe that CuBr oxidizes the alkyl radical, which is produced by the addition of the CF3 radical to the alkene, to the corresponding alkyl cation, which then reacts with the CF3 anion from TMSCF3 to produce the desired product. This reaction tolerates a diverse set of substrates bearing functional groups such as amides, esters, ethers, ketones, protected amines, tertiary amines, and phthalimides; hence this transformation is widely applicable to a wide variety of substrates. (Figure presented.).
- Oh, Hyunseok,Park, Areum,Jeong, Kyu-Sung,Han, Soo Bong,Lee, Hyuk
-
supporting information
p. 2136 - 2140
(2019/03/13)
-
- Synthesis and structure-activity relationships of small-molecular di-basic esters, amides and carbamates as flaviviral protease inhibitors
-
Inhibitors of the flaviviral serine proteases, which are crucial for the replication of dengue and West-Nile virus, have attracted much attention over the last years. A dibasic 4-guanidinobenzoate was previously reported as inhibitor of the dengue protease with potency in the low-micromolar range. In the present study, this lead structure was modified with the intent to explore structure-activity relationships and obtain compounds with increased drug-likeness. Substitutions of the guanidine moieties, the aromatic rings, and the ester with other functionalities were evaluated. All changes were accompanied by a loss of inhibition, indicating that the 4-guanidinobenzoate scaffold is an essential element of this compound class. Further experiments indicate that the target recognition of the compounds involves the reversible formation of a covalent adduct.
- Sundermann, Tom R.,Benzin, Clarissa V.,Dra?i?, Tonko,Klein, Christian D.
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p. 187 - 194
(2019/05/21)
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- N-Phenyl-N-aceto-vinylsulfonamides as Efficient and Chemoselective Handles for N-Terminal Modification of Peptides and Proteins
-
A number of vinylsulfonamides were synthesized and screened to identify reagents that can be used to modify octreotide under biological pH and room temperature with improved efficiency. N-Phenyl-N-aceto-vinylsulfonamide exhibits higher reactivity and has emerged as an efficient reagent that has the ability to realize the selective modification of peptides and proteins at the N-terminus via aza-Michael addition. We showed that, after conjugation of peptides and proteins with the reagent containing a bioorthogonal functional group, the derivatives could be further labelled by functionalities, including fluorescent tags, modified drugs and polyethylene glycol (PEG) polymers without the need for prior treatment. Somatostatin, lysozyme, and RNaseA were selectively modified at the N-terminus, which illustrated the application of the method.
- Huang, Rong,Li, Zhihong,Ren, Peiling,Chen, Wenzhang,Kuang, Yuanyuan,Chen, Jiakang,Zhan, Yuexiong,Chen, Hongli,Jiang, Biao
-
supporting information
p. 829 - 836
(2018/02/21)
-
- Chemoselective: N-tert -butyloxycarbonylation of amines in glycerol
-
A catalyst-free, efficient and green protocol has been developed for the chemoselective N-Boc protection of amines by using glycerol as a solvent at room temperature. A variety of functionalized amines, such as aliphatic, aromatic as well as heteroaromatic were protected using the developed protocol. N-tert-Butyloxycarbonylation derivatives were formed without the formation of isocyanate, urea, N,N-di-t-Boc, or oxazolidinone as side products. The operational simplicity, cleaner reaction, rapid reaction convergence, functional group tolerance, excellent yield, high selectivity, catalyst-free feature and solvent recyclability are the distinct advantages of this protocol. Owing to these merits, this protocol is feasible, economical and environmentally benign.
- Ingale, Ajit P.,More, Vishal K.,Gangarde, Uddhav S.,Shinde, Sandeep V.
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supporting information
p. 10142 - 10147
(2018/06/18)
-
- Synthesis and polymerization of a new hydantoin monomer with three halogen binding sites for developing highly antibacterial surfaces
-
N-Halamine-based antibacterial polymers play a significant role in controlling microbe-associated surface contamination. Hydantoin-containing polymers are usually synthesized by tethering polymerizable moieties to 5,5′-dialkyl hydantoin. However, such app
- Rai, Rajani Kant,Jayakrishnan
-
p. 12152 - 12161
(2018/07/25)
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- One-pot synthesis of diverse: N, N ′-disubstituted guanidines from N -chlorophthalimide, isocyanides and amines via N -phthaloyl-guanidines
-
A sequential one-pot approach towards N,N′-disubstituted guanidines from N-chlorophthalimide, isocyanides and amines is reported. This strategy provides straightforward and efficient access to diverse guanidines in yields up to 81% through previously unprecedented N-phthaloylguanidines. This protocol also features wide substrate scope and mild conditions.
- Demjén, András,Angyal, Anikó,W?lfling, János,Puskás, László G.,Kanizsai, Iván
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supporting information
p. 2143 - 2149
(2018/03/26)
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- Single-Site Labeling of Native Proteins Enabled by a Chemoselective and Site-Selective Chemical Technology
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Chemical biology research often requires precise covalent attachment of labels to the native proteins. Such methods are sought after to probe, design, and regulate the properties of proteins. At present, this demand is largely unmet due to the lack of empowering chemical technology. Here, we report a chemical platform that enables site-selective labeling of native proteins. Initially, a reversible intermolecular reaction places the "chemical linchpins" globally on all the accessible Lys residues. These linchpins have the capability to drive site-selective covalent labeling of proteins. The linchpin detaches within physiological conditions and capacitates the late-stage installation of various tags. The chemical platform is modular, and the reagent design regulates the site of modification. The linchpin is a multitasking group and facilitates purification of the labeled protein eliminating the requirement of additional chromatography tag. The methodology allows the labeling of a single protein in a mixture of proteins. The precise modification of an accessible residue in protein ensures that their structure remains unaltered. The enzymatic activity of myoglobin, cytochrome C, aldolase, and lysozyme C remains conserved after labeling. Also, the cellular uptake of modified insulin and its downstream signaling process remain unperturbed. The linchpin directed modification (LDM) provides a convenient route for the conjugation of a fluorophore and drug to a Fab and monoclonal antibody. It delivers trastuzumab-doxorubicin and trastuzumab-emtansine conjugates with selective antiproliferative activity toward Her-2 positive SKBR-3 breast cancer cells.
- Adusumalli, Srinivasa Rao,Rawale, Dattatraya Gautam,Singh, Usha,Tripathi, Prabhanshu,Paul, Rajesh,Kalra, Neetu,Mishra, Ram Kumar,Shukla, Sanjeev,Rai, Vishal
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supporting information
p. 15114 - 15123
(2018/11/10)
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- Development of a novel protocol for chemoselective deprotection of N/O-benzyloxycarbonyl (Cbz) at ambient temperature
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Abstract: A novel protocol for the deprotection of N-benzyloxycarbonyl and O-benzyloxycarbonyl groups by nickel boride generated in situ from NaBH4 and NiCl2·6H2O in methanol at room temperature has been developed to give the corresponding amines and phenols. This protocol is chemoselective as groups like chloro, bromo, amide, ester, pyridine, and tert-butyloxycarbonyl moiety are unaffected under these conditions. The deprotection has also been validated in gram scale reactions, to establish the wider appropriateness of this protocol. Graphical abstract: [Figure not available: see fulltext.].
- Saroha, Mohit,Aggarwal, Komal,Bartwal, Gaurav,Khurana, Jitender M.
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p. 2231 - 2235
(2018/10/02)
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- Synergistic Photo-Copper-Catalyzed Hydroxylation of (Hetero)aryl Halides with Molecular Oxygen
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Photoredox-mediated copper-catalyzed hydroxylation of (hetero)aryl halides (including chlorides, bromides, and iodides) with O2 at room temperature has been developed. Preliminary mechanistic studies indicate no arylcopper intermediate and that aryl radicals are involved in this procedure. 18O-labeling experiments confirm the hydroxyl oxygen atom originated from molecular oxygen.
- Zhang, Xin,Wu, Ge,Gao, Wenxia,Ding, Jinchang,Huang, Xiaobo,Liu, Miaochang,Wu, Huayue
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supporting information
p. 708 - 711
(2018/02/09)
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- Phenol compound and preparation method
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The invention relates to a phenol compound and a preparation method. In an organic solvent, aryl halide and oxygen or air are used as reaction raw materials, and under the combined facilitation effectof a copper catalyst, alkali and an additive, the aryl halide and the oxygen react in illumination of light to obtain the phenol compound. The copper catalyst and the alkali have key effects in a reaction process. The preparation method of the phenol compound has the advantages of wide substrate range, operation at room temperature, simple aftertreatment, high yield and purity of products and thelike. A new synthetic route and method are opened for the phenol compound, and thus, the phenol compound has good application potential and research value.
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Paragraph 0120-0123
(2018/04/27)
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- Asymmetric Transfer Hydrogenation of 1,3-Alkoxy/Aryloxy Propanones Using Tethered Arene/Ru(II)/TsDPEN Complexes
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A series of propanones containing combinations of aryloxy and alkoxy substituents at the 1- and 3-positions were reduced to the alcohols via asymmetric transfer hydrogenation using a tethered Ru(II)/TsDPEN catalyst. The enantioselectivities of the reductions reveal a complex pattern of electronic and steric effects which, when used in a matched combination, can lead to the formation of products of up to 68% ee (84:16 er) from this highly challenging class of substrate.
- Forshaw, Sam,Matthews, Alexander J.,Brown, Thomas J.,Diorazio, Louis J.,Williams, Luke,Wills, Martin
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supporting information
p. 2789 - 2792
(2017/06/07)
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- Efficient and expeditious chemoselective BOC protection of amines in catalyst and solvent-free media
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A green and eco-friendly route for the almost quantitative BOC protection of a large variety of aliphatic and aromatic amines, amino acids, and amino alcohols is reported in catalyst and solvent-free media under mild reaction conditions. The products were confirmed by 1H, 13C NMR, IR spectroscopy, and in some cases, elemental analysis. This protocol does not require any water quenches, solvent separations, and purification steps, such as recrystallization and column chromatography.
- Viswanadham, Balaga,Mahomed, Abdul S.,Friedrich, Holger B.,Singh, Sooboo
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p. 1355 - 1363
(2017/02/15)
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- A convenient method for multicolour labelling of proteins with BODIPY fluorophores via tyrosine residues
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Fluorescence is an essential imaging modality for labelling and visualising cells and sub-cellular structures. Multicolour labelling is especially challenging due to differences in physicochemical and photophysical behaviour of structurally unrelated fluorophores in the heterogeneous environments found in sub-cellular compartments. Herein, we report the conjugation of three azide-bearing BODIPYs with similar core structures but widely different emission wavelengths (green, red and NIR) to tyrosine residues of a model globular protein (BSA) via a common linking methodology. The resulting BODIPY-BSA conjugates have demonstrated multi-wavelength fluorescence emission for biological applications. Fluorescence imaging was performed in HeLa cells through live cell confocal microscopy imaging, with good intracellular location visualisation observed.
- Cheng, Miffy H.Y.,Savoie, Huguette,Bryden, Francesca,Boyle, Ross W.
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p. 1260 - 1267
(2017/08/16)
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- Divinylsulfonamides as Specific Linkers for Stapling Disulfide Bonds in Peptides
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A new class of N-phenyl-divinylsulfonamides which can be easily prepared have been successfully developed and utilized as efficient linkers in the field of disulfide bond modification. Functional divinylsulfonamides provide opportunities for the specific
- Li, Zhihong,Huang, Rong,Xu, Hongtao,Chen, Jiakang,Zhan, Yuexiong,Zhou, Xianhao,Chen, Hongli,Jiang, Biao
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supporting information
p. 4972 - 4975
(2017/09/23)
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- Divinyl sulfamide linker as well as preparation and application thereof
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The invention provides a divinyl sulfamide linker as well as preparation and an application thereof. The divinyl sulfamide linker has the structural formula shown in the formula I or the formula II. One end of the novel divinyl sulfamide linker can be cou
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Paragraph 0035; 0108; 0109
(2018/03/01)
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- H2 evolution catalyzed by a FeFe-hydrogenase synthetic model covalently attached to graphite surfaces
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A synthetic mimic of Fe-Fe hydrogenase (H2ase) is reported which bears a terminal alkyne group in the ligand. Using a terminal azide bearing organic linkers, this complex could be covalently attached to various electrode surfaces (e.g. edge pla
- Ahmed, Md Estak,Dey, Subal,Mondal, Biswajit,Dey, Abhishek
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p. 8188 - 8191
(2017/07/24)
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- Probing the Hydrophobic Binding Pocket of G-Protein-Coupled Lysophosphatidylserine Receptor GPR34/LPS1 by Docking-Aided Structure-Activity Analysis
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The ligands of certain G-protein-coupled receptors (GPCRs) have been identified as endogenous lipids, such as lysophosphatidylserine (LysoPS). Here, we analyzed the molecular basis of the structure-activity relationship of ligands of GPR34, one of the LysoPS receptor subtypes, focusing on recognition of the long-chain fatty acid moiety by the hydrophobic pocket. By introducing benzene ring(s) into the fatty acid moiety of 2-deoxy-LysoPS, we explored the binding site's preference for the hydrophobic shape. A tribenzene-containing fatty acid surrogate with modifications of the terminal aromatic moiety showed potent agonistic activity toward GPR34. Computational docking of these derivatives with a homology modeling/molecular dynamics-based virtual binding site of GPR34 indicated that a kink in the benzene-based lipid surrogates matches the L-shaped hydrophobic pocket of GPR34. A tetrabenzene-based lipid analogue bearing a bulky tert-butyl group at the 4-position of the terminal benzene ring exhibited potent GPR34 agonistic activity, validating the present hydrophobic binding pocket model.
- Sayama, Misa,Inoue, Asuka,Nakamura, Sho,Jung, Sejin,Ikubo, Masaya,Otani, Yuko,Uwamizu, Akiharu,Kishi, Takayuki,Makide, Kumiko,Aoki, Junken,Hirokawa, Takatsugu,Ohwada, Tomohiko
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supporting information
p. 6384 - 6399
(2017/08/02)
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- Sustainable and chemoselective N-Boc protection of amines in biodegradable deep eutectic solvent
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Abstract: A green and practical approach for the chemoselective N-tert-butyloxycarbonylation of structurally diverse amines with di-tert-butyl dicarbonate (Boc2O) is described. Selective N-Boc protection was achieved in excellent yields in urea-choline chloride deep eutectic solvent (DES) as the most promising environmentally benign and cost-effective solvent under mild reaction condition. DES can protect various aromatic and aliphatic amines using Boc2O in good to excellent yields in short reaction times without any side products. Graphical abstract: [Figure not available: see fulltext.].
- Azizi, Najmedin,Shirdel, Fatemeh
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p. 1069 - 1074
(2017/05/12)
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- MULTI-FUNCTIONAL CHEMICAL AGENTS, AND THE METHOD FOR PROTEIN MODIFICATION
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A multifunctional chemical agents comprising functional agents Fn1, Fn2 and linkers, for the linchpin directed (LDM), protein directed (PDPM) modifications of proteins, and Fn1 accelerated kinetic labeling by Fn2.
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Page/Page column 26
(2017/10/11)
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- Metal-Free One-Pot Synthesis of N,N′-Diarylamidines and N-Arylbenzimidazoles from Arenediazonium Salts, Nitriles, and Free Anilines
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A highly efficient and facile metal-free, one-pot reaction has been developed to afford diversely substituted N-arylbenzimidazoles through chemoselective in situ generation of N,N′-diarylamidines from arenediazonium salts, nitriles, and free anilines. The advantages of this protocol consist of the operationally easy and simple one-pot procedure under metal-free and mild conditions, the direct use of inexpensive and commercially available chemicals, and thus, a cost-effective and greener process.
- Youn, So Won,Lee, Eun Mi
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supporting information
p. 5728 - 5731
(2016/11/17)
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- Efficient N-Boc protection of amines by a reusable heterogeneous solid acid nanocatalyst at room temperature
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An efficient and rapid protocol for chemoselective N-Boc protection of various structurally different aryl, aliphatic, and heterocyclic amines is reported with (Boc)2O using mesoporous silica phenylsulfonic acid (SBA-15-Ph-SO3H) as a recyclable and heterogeneous solid acid nanocatalyst under solvent-free condition at ambient temperature. The catalyst can be easily recovered and reused for ten reaction cycles for protection of amines without considerable loss of activity. The advantages of this green method are simplicity, easy workup, chemoselectivity, short reaction time, and excellent yield.
- Veisi, Hojat,Sedrpoushan, Alireza,Ghazizadeh, Habibollah,Hemmati, Saba
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p. 1451 - 1461
(2016/04/26)
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- Heterobimetallic dinuclear lanthanide alkoxide complexes as acid-base bifunctional catalysts for synthesis of carbamates under solvent-free conditions
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Heterobimetallic dinuclear lanthanide alkoxide complexes Ln2Na8(OCH2CH2NMe2)12(OH)2 [Ln: I (Nd), II (Sm), III (Yb) and IV (Y)] were used as efficient acid-base bifunctional catalysts for the synthesis of carbamates from dialkyl carbonates and amines as well as the N-Boc protection of amines. The cooperative catalysts showed high catalytic activity and a wide scope of substrates with good to excellent yields under solvent-free conditions. The systems have shown higher catalytic activities due to the noteworthy synergistic interactions of Lewis acid center-Br?nsted basic center. The comparison of catalytic efficiency between mono- and dinuclear heterobimetallic lanthanide alkoxide analogues was also investigated.
- Zeng, Ruijie,Bao, Linquan,Sheng, Hongting,Sun, Lili,Chen, Man,Feng, Yan,Zhu, Manzhou
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p. 78576 - 78584
(2016/09/09)
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