- Palladium-catalyzed ortho-C(sp2)[sbnd]H bromination of benzaldehydes via a monodentate transient directing group strategy
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A facile and efficient monodentate transient directing group strategy was developed to enable the palladium-catalyzed ortho-C(sp2)[sbnd]H bromination of benzaldehydes. A broad scope of benzaldehydes were transformed into the desired products by employing 2-amino-5-chlorobenzotrifluoride as a monodentate transient directing group, demonstrating good functional group tolerance. Mild reaction conditions and no requirement for a silver salt are also features of this strategy.
- Yong, Qiyun,Sun, Bing,Zhang, Fang-Lin
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supporting information
(2019/11/03)
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- Method for preparing 2-bromo-5-chlorobenzaldehyde
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The invention discloses a method for preparing 2-bromo-5-chlorobenzaldehyde. The method is characterized by comprising the following steps: a, controlling the system temperature to be less than or equal to 10 DEG C, and sequentially and slowly dropwise adding 3-chlorobenzaldehyde and an iodine-containing catalyst in an inorganic strong-acid solvent; b, controlling the system temperature to be lessthan or equal to 15 DEG C, and adding N-bromosuccinimide NBS for multiple times in batches; and c, insulating to react for 2-10 hours, heating to 25-55 DEG C to keep on reacting for 1-6 hours, and performing post-treatment to obtain a solid product. The method has the advantages of one-step reaction, 90% high yield, simple operation, low cost, easily available raw materials, environmental friendliness and little pollution, and is suitable for the requirement for large-scale industrial production since only acid liquid is contained in waste liquid and can be neutralized in alkali liquor.
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Paragraph 0034-0037; 0058-0065; 0070-0085
(2018/04/26)
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- Synthesis of functionalized helical BN-benzo[c] phenanthrenes
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A novel parent BN-benzo[c]phenanthrene, with helical chirality and remarkable structural features, has been easily obtained in three steps with a global yield of 55%. Moreover, Cl-substituted derivatives have been prepared and these have served as useful starting materials for the development of palladium-catalyzed cross-coupling reactions.
- Abengózar, Alberto,García-García, Patricia,Sucunza, David,Pérez-Redondo, Adrián,Vaquero, Juan J.
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supporting information
p. 2467 - 2470
(2018/03/21)
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- Diverse ortho-C(sp2)-H functionalization of benzaldehydes using transient directing groups
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Pd-catalyzed C-H functionalizations promoted by transient directing groups remain largely limited to C-H arylation only. Herein, we report a diverse set of ortho-C(sp2)-H functionalizations of benzaldehyde substrates using the transient directing group strategy. Without installing any auxiliary directing group, Pd(II)-catalyzed C-H arylation, chlorination, bromination, and Ir(III)-catalyzed amidation, could be achieved on benzaldehyde substrates. The transient directing groups formed in situ via imine linkage can override other coordinating functional groups capable of directing C-H activation or catalyst poisoning, significantly expanding the scope for metal-catalyzed C-H functionalization of benzaldehydes. The utility of this approach is demonstrated through multiple applications, including late-stage diversification of a drug analogue.
- Liu, Xi-Hai,Park, Hojoon,Hu, Jun-Hao,Hu, Yan,Zhang, Qun-Liang,Wang, Bao-Long,Sun, Bing,Yeung, Kap-Sun,Zhang, Fang-Lin,Yu, Jin-Quan
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supporting information
p. 888 - 896
(2017/05/16)
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- A gold catalytic oxidation of benzyl alcohol synthesis method (by machine translation)
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The present invention provides a kind of organic synthesis in the oxidation of benzyl alcohol synthesis method, the reaction formula is as follows, in the formula 1 containing different substituents is benzyl alcohol, in the formula 2 is triphenylcarbinol compound. The required reaction of gold catalyst is Ph3 PAuCl, Ph3 PAuNTf2 , HAuCl4 , NaAuCl4 , Ph3 PAuOTf, Ph3 PAuSbF6 , IPrAuCl, gold. The required reaction medium is: solvent-free, toluene, are three-toluene, 1, 2 - dichloroethane, tetrahydrofuran, acetonitrile, acetone. The reaction implementing microwave heating of reactor, the method of the invention the oxidizing agent triphenylcarbinol for commercial products, cheap, and simple experimental operation, substrate and wide range of application. (by machine translation)
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Paragraph 0034-0037; 0041; 0055-0057
(2017/08/25)
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- 15-aryl prostaglandins as EP4 agonists, and methods of use thereof
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The invention provides compositions and methods for reducing healing wounds and reducing scars and blemishes. The compositions and methods of the invention include at least one EP4 agonist set forth herein. Wounds and or scars that can be treated by the compositions and methods of the invention can arise from events such as surgery, trauma, disease, mechanical injury, burn, radiation, poisoning, and the like.
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Page/Page column 68
(2017/01/31)
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- Fe(III)-catalyzed trityl benzyl ether formation and disproportionation cascade reactions to yield benzaldehydes
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During investigating water-compatible Lewis acids catalyzed etherifications using alcohols as alkylating reagents directly, we developed Fe(III)-catalyzed trityl benzyl ether formations irradiated by microwave. Then an in situ trityl benzyl ether formation and disproportionation cascade reaction was achieved to yield the benzaldehyde products with good functional group tolerances under neat conditions at relative higher temperatures. The substituent effects of the substrates on the etherification and disproportionation were explored by changing the substitutions on benzyl alcohols and triarylmethanols using chemical kinetic plots methods and the mechanism of the transformation was studied by crossover experiments. The etherification and disproportionation cascade process could be conveniently scaled up in laboratory without losing much efficiency.
- Wang, Xiaoyu,Du, Chuan,Shi, Hui,Pang, Yadong,Jin, Shengfei,Hou, Yuqian,Wang, Yanshi,Peng, Xiaoshi,Xiao, Jianyong,Liu, Yang,Liu, Yongxiang,Cheng, Maosheng
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p. 6744 - 6748
(2015/08/24)
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- Synthesis and antimicrobial activity of azepine and thiepine derivatives
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A series of new pyridobenzazepine and pyridobenzothiepine derivatives was synthesized by Pd-catalyzed formation of C-N and C-S bonds. All synthesized compounds were tested for their in vitro antimicrobial activity. The pyridobenzazepine derivatives showed better antibacterial and antifungal activity than the corresponding dipyridoazepine analogue. Among the synthesized azepines, derivative 8 displayed potent activity against the tested bacteria (MIC ranged 39-78 μg mL-1), while azepine 12 showed promising antifungal activity (MIC ranged 156-313 μg mL-1). The synthesized thiepine derivatives exhibited weak antibacterial activity, but showed pronounced antifungal activity.
- Boinovi, Nina,Novakovi, Irena,Rajai, Sladana Kosti,Opsenica, Igor M.,olaja, Bogdan A.
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p. 839 - 852
(2015/08/24)
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- 6,12-DINAPHTHYLCHRYSENE DERIVATIVE AND ORGANIC LIGHT-EMITTING DEVICE USING THE DERIVATIVE
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Provided are an organic compound having high heat stability suitable for use in an organic light-emitting device, and an organic light-emitting device using the organic compound. The organic light-emitting device is an organic light-emitting device, including: an anode; a cathode; and an organic compound layer disposed between the anode and the cathode, in which at least one layer of the organic compound layer has a 6,12-dinaphthylchrysene derivative represented by one of the following general formulae (1) and (2): in the formulae (1) and (2), Z represents a naphthyl group, and Q represents an electron-withdrawing substituent selected from the group consisting of the following general formulae (3) to (5): in the formula (5), R1 represents a hydrogen atom or a methyl group.
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- DEVICES FOR HIGH-FREQUENCY TECHNOLOGY, LIQUID-CRYSTALLINE MEDIA AND COMPOUNDS
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The present invention relates to a device for high-frequency technology, or for the microwave region and millimetre wave region of the electromagnetic spectrum, characterised in that it contains a liquid-crystal medium which consists of one or more compounds, which one or more compounds, which contain 6 to 15 five-, six- or seven-membered rings, preferably 1,4-linked phenylene rings, or in that it contains a liquid-crystal medium which itself comprises a component A, which itself consists of one or more of the said compounds, which one or more compounds, which contain 6 to 15 five-, six- or seven-membered rings, preferably 1,4-linked phenylene rings. The present invention additionally relates to compounds of the formula (I), in which the parameters have the meanings given in the text, and to the corresponding, novel liquid-crystal media, to the use and preparation thereof, and to the production and use of the devices. The devices according to the invention are particularly suitable phase shifters in the microwave and millimetre wave region, for microwave and millimetre wave array antennas and very particularly for so-called tunable “reflectarrays”.
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- Selective ortho -bromination of substituted benzaldoximes using Pd-catalyzed C-H activation: Application to the synthesis of substituted 2-bromobenzaldehydes
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Substituted 2-bromobenzaldehydes were synthesized from benzaldehydes using a three-step sequence involving a selective palladium-catalyzed ortho-bromination as the key step. O-Methyloxime serves as a directing group in this reaction. A rapid deprotection of substituted 2-bromobenzaldoximes afforded substituted 2-bromobenzaldehydes with good overall yields.
- Dubost, Emmanuelle,Fossey, Christine,Cailly, Thomas,Rault, Sylvain,Fabis, Frederic
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experimental part
p. 6414 - 6420
(2011/09/16)
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- Inter- and intramolecular hydroacylation of alkenes employing a bifunctional catalyst system
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Based on a conceptually innovative bifunctional P,N ligand, an efficient protocol for the rhodium-catalyzed inter- and intramolecular hydroacylation of alkenes has been developed.
- Vautravers, Nicolas R.,Regent, Damien D.,Breit, Bernhard
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supporting information; experimental part
p. 6635 - 6637
(2011/06/27)
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- Hydrogen-bonding catalysis and inhibition by simple solvents in the stereoselective kinetic epoxide-opening spirocyclization of glycal epoxides to form spiroketals
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Mechanistic investigations of a MeOH-induced kinetic epoxide-opening spirocyclization of glycal epoxides have revealed dramatic, specific roles for simple solvents in hydrogen-bonding catalysis of this reaction to form spiroketal products stereoselectively with inversion of configuration at the anomeric carbon. A series of electronically tuned C1-aryl glycal epoxides was used to study the mechanism of this reaction based on differential reaction rates and inherent preferences for SN2 versus SN1 reaction manifolds. Hammett analysis of reaction kinetics with these substrates is consistent with an SN2 or SN2-like mechanism (ρ = -1.3 vs ρ = -5.1 for corresponding SN1 reactions of these substrates). Notably, the spirocyclization reaction is second-order dependent on MeOH, and the glycal ring oxygen is required for second-order MeOH catalysis. However, acetone cosolvent is a first-order inhibitor of the reaction. A transition state consistent with the experimental data is proposed in which one equivalent of MeOH activates the epoxide electrophile via a hydrogen bond while a second equivalent of MeOH chelates the side-chain nucleophile and glycal ring oxygen. A paradoxical previous observation that decreased MeOH concentration leads to increased competing intermolecular methyl glycoside formation is resolved by the finding that this side reaction is only first-order dependent on MeOH. This study highlights the unusual abilities of simple solvents to act as hydrogen-bonding catalysts and inhibitors in epoxide-opening reactions, providing both stereoselectivity and discrimination between competing reaction manifolds. This spirocyclization reaction provides efficient, stereocontrolled access to spiroketals that are key structural motifs in natural products.
- Wurst, Jacqueline M.,Liu, Guodong,Tan, Derek S.
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supporting information; experimental part
p. 7916 - 7925
(2011/07/08)
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- Synthesis and fungicidal activities of novel indene-substituted oxime ether strobilurins
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Nineteen novel indene-substituted oxime ether strobilurins, which used an indene group to stabilize the (E)-styryl group in SYP-Z071 (an unsaturated oxime strobilurin fungicide under development by the Shenyang Research Institute of Chemical Industry), were designed and synthesized. The biological assay results showed that all compounds possessed good or excellent fungicidal activities. It was found that most of the compounds showed higher fungicidal activities against Pyricularia oryzae, Phytophthora infestans, Erysiphe graminis, and Colletotrichum lagenarium than SYP-Z071 at the tested concentration. The biological assay results also indicated that most of the compounds exhibited higher in vivo fungicidal activities against cucumber Pseudoperonospora cubensis and C. lagenarium than the commercial fungicides trifloxystrobin and kresoxim-methyl at a concentration of 6.25 mg/L. Furthermore, it was found that α-(methoxyimino)-N-methylphenylacetamide oxime ethers 6m-s exhibited a broad spectrum and remarkably higher activities against all tested fungi. Especially, the 6-methylindene-substituted compound 6p was identified as the most promising candidate for further study.
- Tu, Song,Xu, Long-He,Ye, Li-Yi,Wang, Xi,Sha, Yong,Xiao, Zong-Yuan
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experimental part
p. 5247 - 5253
(2010/04/06)
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- TETRACYCLIC INDOLE DERIVATIVES AS ANTIVIRAL AGENTS
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The present invention relates to tetracyclic indole compounds of formula (I); wherein R1, R2, A, Ar, W, X, Y and Z are defined herein, and pharmaceutically acceptable salts thereof, pharmaceutical compositions comprising them, and their use for the treatment or prevention of infection by hepatitis C virus.
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Page/Page column 28
(2010/11/08)
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- Diversity-oriented synthesis of biaryl-containing medium rings using a one bead/one stock solution platform
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Diversity-oriented synthesis of structurally complex and diverse small molecules can be used as the first step in a process to explore cellular and organismal pathways. The success of this process is likely going to be dependent on advances in the synthesis of small molecules having natural product-like structures in an efficient and stereoselective manner. The development, scope, and mechanism of the oxidation of organocuprates was investigated and exploited in the atropdiastereoselective synthesis of biaryl-containing medium rings (9-, 10-, and 11-membered rings). The methodology was performed on high-capacity, large polystyrene beads by metalating aryl bromides with-iPrBu2MgLi, followed by transmetalating with CuCN·2LiBr and then oxidizing with 1,3-dinitrobenzene, and was used in a diversity-oriented synthesis of biaryl-containing medium rings (library total theoretical maximum 1412 members). The high capacity beads were arrayed into 384-well plates and, using a process optimized during the development of a one bead/one stock solution technology platform, converted into arrays of stock solutions, with each stock solution containing largely one compound. These stock solutions were used in numerous phenotypic and proteinbinding assays. The process described outlines a pathway that we feel will contribute to a comprehensive and systematic chemical approach to exploring biology (chemical genetics).
- Spring, David R.,Krishnan, Shyam,Blackwell, Helen E.,Schreiber, Stuart L.
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p. 1354 - 1363
(2007/10/03)
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- Azolyl methyl phenyl derivatives having aromatase inhibitory activity
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Compounds exerting excellent aromatase inhibitory activity in vivo and in vitro with higher specificity and greater safety are provided together with the salts thereof. Using the same, there are also provided, prophylactic agents and/or therapeutical agents of estrogen-dependent diseases, contraceptive agents for females, and aromatase inhibitory agents for use in the form of reagents for human or animals. The compounds are of the formula (I), wherein R2 is represented by the formula (II) or (III). (I) (II) or
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