- Design, synthesis and structure of a frustrated benzoxaborole and its applications in the complexation of amines, amino acids, and protein modification
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This study describes the design and synthesis of arylboronic acid 2, the first example of a permanently open "frustrated" benzoxaborole, along with an exploration of its application in bioconjugation. An efficient and high yielding seven-step synthesis was optimized. NMR experiments confirmed that compound 2 exists in the open ortho-hydroxyalkyl arylboronic acid structure 2-I, a form that is effectively prevented to undergo a dehydrative cyclization as a result of unfavorable geometry. Compound 2-I conjugates effectively with amines to form stable hemiaminal ether structures, including a highly effective reaction with lysozyme. Complexation with cysteine induces an open structure containing a free hydroxymethyl arm, with the amino and thiol groups reacting preferentially with the formyl group to form a N,S-acetal.
- Bhangu, Jasmine,Hall, Dennis G.,Whittal, Randy M.
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Read Online
- Preparation process 2-6 - dibromobenzoyl chloride
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The invention discloses a preparation process for 2,6-dibromobenzene methylsulfonyl chloride. The preparation process comprises the following steps: with m-dibromobenzene as a starting raw material, subjecting the m-dibromobenzene to a five-step reaction of acylation, reduction, chlorine substitution, substitution and sulfonyl chlorination so as to obtain a target compound namely the 2,6-dibromobenzene methylsulfonyl chloride. The process provided by the invention uses cheap and easily-available raw materials, has good safety by using NCS to replace chlorine gas as a chlorinating agent, and facilitates practical application.
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Paragraph 0009; 0016-0018; 0029-0031; 0042-0044; 0054-0056;
(2021/01/24)
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- Functional Porphyrinic Metal–Organic Framework as a New Class of Heterogeneous Halogen-Bond-Donor Catalyst
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Biomimetic metal-organic frameworks have attracted great attention as they can be used as bio-inspired models, allowing us to gain important insights into how large biological molecules function as catalysts. In this work, we report the synthesis and utilization of such a metal-metalloporphyrin framework (MMPF) that is constructed from a custom-designed ligand as an efficient halogen bond donor catalyst for Diels–Alder reactions under ambient conditions. The implementation of fabricated halogen bonding capsule as binding pocket with high-density C?Br bonds enabled the use of halogen bonding to facilitate organic transformations in their three-dimensional cavities. Through combined experimental and computational studies, we showed that the substrate molecules diffuse through the pores of the MMPF, establishing a host-guest system via the C?Br???π interaction. The formation of halogen bonds is a plausible explanation for the observed boosted catalytic efficiency in Diels–Alder reactions. Moreover, the unique capability of MMPF highlights new opportunities in using artificial non-covalent binding pockets as highly tunable and selective catalytic materials.
- Chen, Yu-Sheng,Cheng, Qigan,Ma, Shengqian,Nafady, Ayman,Shan, Chuan,Wojtas, Lukasz,Zhang, Weijie,Zhang, X. Peter
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supporting information
p. 24312 - 24317
(2021/10/04)
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- Photophysical Properties of Silyl-Substituted Stilbene Derivatives
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The effects of silyl groups on the structural, absorption, fluorescence, and photoisomerization properties of stilbenes were investigated. In comparison to that of the parent stilbene (1), fluorescence quantum yields (Φf) of Me3Si-substituted stilbenes 2–4 and 6 in solution were higher. Derivative 5, in which Me3Si groups are present at all ortho positions of the arene moieties, did not fluoresce at room temperature. The absorption and fluorescence wavelength maxima of Me3SiMe2Si-substituted stilbene 7 occurred at longer wavelengths compared to those of the Me3Si analog 2. The results of theoretical calculations showed that this difference is a consequence of an increase in the HOMO energy of 7 caused by orbital interaction between π-system and the σ(Si–Si) orbital. Stilbene 14, with two Me3Si-C≡C groups at both para positions, had a high Φf (0.95). The calculated transition dipole moment (μ) was well correlated with Φf. Derivative 21, which contains Ph2N and Me3SiC≡C groups exhibited solvatofluorochromism because it possesses a twisted intramolecular charge transfer (TICT) excited state in which the Ph2N group and the aromatic ring are orthogonal.
- Maeda, Hajime,Horikoshi, Ryo,Yamaji, Minoru,Furuyama, Taniyuki,Segi, Masahito
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supporting information
p. 3410 - 3422
(2020/06/17)
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- ISOCHROMAN COMPOUNDS AND USES THEREOF
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Compounds of Formula I are described, as are pharmaceutical compositions containing such compounds. Methods of treating neurological or psychiatric diseases and disorders in a subject in need are also disclosed.
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Paragraph 0387; 0389-0390
(2019/02/15)
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- Cysteine feed additive and preparation method thereof
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The invention discloses a cysteine feed additive and a preparation method thereof, and belongs to the technical field of synthesis of feed additives. The technical scheme of the invention is as shownin specification. Compared with the prior art, the cysteine feed additive has the beneficial effects that the synthetic method of the invention is simple, a molecular structure is novel, and the cysteine feed additive can serve as an active methionine source, can act on nickel ions in urease protein target spots, has a certain inhibition effect on urease, and is expected to be further popularizedand used as a composite feed additive.
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Paragraph 0017-0028
(2019/03/15)
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- Method for preparing 2, 6-dibromobenzaldehyde
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The invention discloses a method for preparing 2, 6-dibromobenzaldehyde, and belongs to the technical field of organic synthesis. According to the key points of the technical scheme: benzene sulfonicacid is used as a raw material, selective bromination is firstly carried out, substitution reaction is carried out on N, N-dimethyl formamide, and finally the sulfonic acid group is removed to obtainthe 2, 6-dibromobenzaldehyde. Compared with the prior art, the method has the advantages that the synthesis method is simple, the raw materials are low in price, and industrial production is facilitated.
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Paragraph 0029-0040
(2019/03/23)
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- 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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- NOVEL ORGANIC HETEROCYCLIC COMPOUND AND LIGHT-EMITTING DEVICE COMPRISING SAME
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The present invention relates to an organic light-emitting compound represented by [Chemical Formula A] and an organic light-emitting device. In Chemical Formula, A, X, Y, Z, and the substituents R1 to R8, and R11 to R20 are as defined in the specification.
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Paragraph 0106-0107
(2018/03/28)
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- MODULATORS OF CYSTIC FIBROSIS TRANSMEMBRANE CONDUCTANCE REGULATOR
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The present invention features a compound of formula I: or a pharmaceutically acceptable salt thereof, where R1, R2, R3, W, X, Y, Z, n, o, p, and q are defined herein, for the treatment of CFTR mediated diseases, such as cystic fibrosis. The present invention also features pharmaceutical compositions, method of treating, and kits thereof.
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Page/Page column 805-806
(2021/02/10)
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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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- Modulators of Cystic Fibrosis Transmembrane Conductance Regulator
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The present invention features a compound of formula I: or a pharmaceutically acceptable salt thereof, where R1, R2, R3, W, X, Y, Z, n, o, p, and q are defined herein, for the treatment of CFTR mediated diseases, such as cystic fibrosis. The present invention also features pharmaceutical compositions, method of treating, and kits thereof.
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Paragraph 2877; 2878
(2016/05/02)
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- Nonplanar Butterfly-Shaped π-Expanded Pyrrolopyrroles
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Large aza-analogues of curved polycyclic aromatic hydrocarbons with a double-helicene structure present unique features for molecular photonics. We present the preparation and characterization of three such structures. The synthesis of these heterocyclic nanographenes involves only a few high-yield steps that use readily available starting materials. X-ray analysis revealed that each of these new dyes has three conformational isomers: one diastereoisomer in a meso form and two enantiomers in twisted forms [(P,P)] and [(M,M)]. The low energy barriers between the conformers, however, prevent their separation by using chiral HPLC, and the NMR spectra show only one set of signals for each of these curved compounds. Density functional theory (DFT) calculations quantify the small energy difference and the small energy barriers between the chiral and meso forms, which fully supports the experimental results. Their optical absorption lacks any sensitivity to the solvent environment, whereas their fluorescence features exhibit pronounced solvatochromism. This rarely observed solvatofluorochromism of centrosymmetric molecules without either electron-withdrawing groups or -donating substituents was probed by using time-resolved spectroscopy. These studies suggest that, similar to 9,9′-bianthryl, the nonpolar locally excited state shows negligible solvatochromism, whereas the charge-transfer state is sensitive to solvent polarity.
- Krzeszewski, Maciej,Kodama, Takuya,Espinoza, Eli M.,Vullev, Valentine I.,Kubo, Takashi,Gryko, Daniel T.
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p. 16478 - 16488
(2016/11/09)
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- A triazole-bearing picket fence type nickel porphyrin as a cyanide selective allosteric host
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A triazole-bearing picket fence type nickel porphyrin (1) has been synthesized as a host compound for anion binding. Among the various anionic species examined, cyanide was the only one that affected a spectral change of 1. Moreover, 1 exhibited strong homotropic positive allosterism against cyanide binding due to an electronic effect as well as multiple hydrogen bonds formed between cyanide and the triazole groups. This journal is
- Hong, Kyeong-Im,Yoon, Hongsik,Jang, Woo-Dong
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supporting information
p. 7486 - 7488
(2015/05/04)
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- Development of a scalable synthesis of a Bruton's tyrosine kinase inhibitor via C-N and C-C bond couplings as an end game strategy
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A scalable and convergent synthesis of a BTK (Bruton's tyrosine kinase) inhibitor has been developed. Synthetic routes to key intermediates were explored for the scale-up campaign, especially the process for 6-dimethylaminodihydroisoquinolinone, which was prepared via a regioselective cyclization of an isocyanate, mediated by AlCl3. Improved routes to key building blocks were demonstrated by expedient multikilogram productions. The target compound was assembled through a Pd-catalyzed amidation reaction followed by a Suzuki-Miyaura cross-coupling reaction.
- Hong, Jun Bae,Davidson, James P.,Jin, Qingwu,Lee, Gary R.,Matchett, Michael,O'Brien, Erin,Welch, Michael,Bingenheimer, Bill,Sarma, Keshab
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p. 228 - 238
(2014/05/20)
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- Crystal engineering of a microporous, catalytically active fcu topology MOF using a custom-designed metalloporphyrin linker
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A 12-connected fcu metal-organic framework (MOF), MMPF-3, has been prepared using a CoII metalloporphyrin. MMPF-3 is comprised of the same polyhedral supermolecular building blocks as the prototypal fcu-MOF, fcu-MOF-1, and its nanoscale cavities feature 18 catalytically active cobalt centers. The high density (ca. 5 cobalt sites/nm3) affords MMPF-3 superior performance in catalytic epoxidation of trans-stilbene compared to other MOFs. Copyright
- Meng, Le,Cheng, Qigan,Kim, Chungsik,Gao, Wen-Yang,Wojtas, Lukasz,Zaworotko, Michael J.,Zhang, X. Peter,Ma, Shengqian,Chen, Yu-Sheng
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supporting information
p. 10082 - 10085,4
(2020/09/09)
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- Preparation of phenalenes and hydronaphthacenes through tandem alkyne Fischer-carbene complex coupling and inter- or intra-molecular Diels-Alder reactions
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The rapid construction of phenalenes through the reaction of 8-alkynyltetralones with Fischer-carbene complexes followed by either an inter- or intra-molecular Diels-Alder reaction is presented. As a showcase of the synthetic utility of this process, the rapid construction of polycyclic ring systems containing the tetracycline core has been demonstrated through an iterative application of this reaction sequence.
- Patti, Rajesh Kumar,Duan, Shaofeng,Wang, Zhipeng,Herndon, James W.
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scheme or table
p. 4182 - 4185
(2011/09/19)
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- TRICYCLIC HETEROCYCLIC DERIVATIVES
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The present invention relates to a tricyclic heterocyclic derivative of Formula (I) wherein the variables are as defined in the specification. The present invention further relates to pharmaceutical compositions comprising these compounds and to their use in therapy, in particular for the treatment of serotonin-mediated disorders such as obesity, schizophrenia and cognitive dysfunction.
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Page/Page column 103
(2009/04/25)
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- Design and synthesis of 2-(2,6-dibromophenyl)-3-heteroaryl-1,3-thiazolidin-4-ones as anti-HIV agents
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A series of 2-(2,6-dibromophenyl)-3-heteroaryl-1,3-thiazolidin-4-ones were designed, synthesized and evaluated as selective human immunodeficiency virus type-1 reverse transcriptase (HIV-1 RT) enzyme inhibitors. The results of the HIV-1 RT kit and in vitro cell based assay showed that eight compounds effectively inhibited HIV-1 replication at 20-320 nM concentrations with minimal cytotoxicity in MT-4 as well as in CEM cells.
- Rawal, Ravindra K.,Tripathi, Rajkamal,Katti,Pannecouque, Christophe,De Clercq, Erik
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experimental part
p. 2800 - 2806
(2009/04/05)
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- New cyclopentadienyl, indenyl or fluorenyl substituted phosphine compounds and their use in catalytic reactions
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The invention is directed to a phosphine compound represented by general formula (1) wherein R' and R" independently are selected from alkyl, cycloalkyl and 2-furyl radicals, or R' and R" are joined together to form with the phosphorous atom a carbon-phosphorous monocycle comprising at least 3 carbon atoms or a carbon-phosphorous bicycle; the alkyl radicals, cycloalkyl radicals, and carbon-phosphorous monocycle being unsubstituted or substituted by at least one radical selected from the group of alkyl, cycloalkyl, aryl, alkoxy, and aryloxy radicals; Cps is a partially substituted or completely substituted cyclopentadien-1-yl group, including substitutions resulting in a fused ring system, and wherein a substitution at the 1-position of the cyclopentadien-1-yl group is mandatory when the cyclopentadien-1-yl group is not part of a fused ring system or is part of an indenyl group. Also claimed is the use of these phosphines as ligands in catalytic reactions and the preparation of these phosphines.
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Page/Page column 35
(2008/06/13)
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- 9-Fluorenylphosphines for the Pd-catalyzed Sonogashira, Suzuki, and Buchwald-Hartwig coupling reactions in organic solvents and water
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The lithiation/alkylation of fluorene leads to various 9-alkyl-fluorenes (alkyl = Me. Et, /Pr, -Pr. -C18H25) in > 95% yields, for which lithiation and reaction with R2PCl (R = Cy, iPr, tBu) generates 9-alkyl, 9-PR2fluorenes which constitute electron-rich and bulky phosphine ligands. The in-situ-formed palladium-phosphinc complexes ([Na2PdCl4], phosphonium salt, base, substrates) were tested in the Sonogashira. Suzuki, and Buchwald-Hartwig reactions of aryl chlorides and aryl bromides in organic solvents. The Sonogashira coupling of aryl chlorides at 100-120°C leads to >90% yields with 1 mol % of Pd catalyst. The Suzuki coupling of aryl chlorides typically requires 0.05 mol % of Pd catalyst at 100°C in dioxane for quantitative product formation. To carry out "green" cross-coupling reactions in water, 9-ethylfluorenyldicyclohexylphosphine was reacted in sulphuric acid to generate the respective 2-sulfonated phosphonium salt. The Suzuki coupling of activated aryl chlorides by using this water-soluble catalyst requires only 0.01 mol% of Pd catalyst, while a wide range of aryl chlorides can be quantitatively converted into the respective coupling products by using 0.1-0.5 mol % of catalyst in pure water at 100°C. Difficult substrate combinations, such as naphthylboronic acid or 3-pyridylboronic acid and aryl chlorides are coupled at 100°C by using 0.1-0.5 mol % of catalyst in pure water to obtain the respective N-heterocycles in quantitative yields. The copper-free aqueous Sonogashira coupling of aryl bromides generates the respective tolane derivatives in > 95 % yield.
- Fleckenstein, Christoph A.,Plenio, Herbert
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p. 2701 - 2716
(2008/03/14)
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- Chiral porphyrins, chiral metalloporphyrins, and methods for synthesis of the same
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Novel methods of synthesizing heteroatom-containing chiral porphyrins and chiral metalloporphyrins and the novel chiral porphyrins and chiral metalloporphyrins themselves are disclosed. Metal complexes of the chiral porphyrins are prepared in high yields and shown to be active catalysts for highly enantioselective and diastereoselective cyclopropanation, aziridination, and epoxidation of alkenes under a practical one-pot protocol.
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- Regiospecific metalation of oligobromobenzenes
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The metalation of selected oligobromobenzenes with lithium diisopropylamide (LDA) was investigated. 1,3-Dibromo-substituted benzenes were metalated without special precautions since the resultant 2,6-dibromophenyllithium intermediates are relatively stabl
- Lulinski, Sergiusz,Serwatowski, Janusz
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p. 5384 - 5387
(2007/10/03)
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- Synthesis, absorption and luminescence of a new series of soluble distyrylbenzenes featuring cyano substituents at the peripheral rings
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The synthesis of a complete series of nine soluble distyrylbenzenes (DSBs) with two (2a-c) and four cyano groups (1a-f) attached to the peripheral aromatic rings is reported. They were prepared by the Wittig reaction and characterized by 1H and 13C NMR, FT-IR, UV/Vis, PL, EL, mass spectra, and elemental analysis. The optical properties have been studied in detail to monitor structure-luminescence relationships as a function of the position of the cyano moieties. The DSBs with cyano substituents show bathochromic shifts in their absorption spectra when compared to the parent DSB (30). The extent of this red-shift depends on electronic and steric factors. The bis(p-cyano)-substituted compound 2c exhibits a small Stokes shift and a remarkably high quantum yield of ψF = 0.6-0.8 in the solid state. All the new distyrylbenzenes show electroluminescence when employed in devices with an ITO/PcCu/DSB/Al configuration and with colors ranging from red to green.
- Schweikart, Karl-Heinz,Hanack, Michael,Lueer, Larry,Oelkrug, Dieter
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p. 293 - 302
(2007/10/03)
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