- Programmed Negative Allostery with Guest-Selected Rotamers Control Anion-Anion Complexes of Stackable Macrocycles
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A new rotamer-based strategy for negative allostery has been used to control host-host interactions and product yield upon anion complexation. Coassembly of anion dimers as guests inside two cyanostar macrocycles drives selection of one rotamer in which all ten steric groups get directed outward to destabilize triply stacked macrocycles. A large entropy penalty (ΔS) is quantified upon anion binding when the multiple dynamic rotamers collapse down to one.
- Sheetz, Edward G.,Qiao, Bo,Pink, Maren,Flood, Amar H.
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Read Online
- Understanding the Activation of Air-Stable Ir(COD)(Phen)Cl Precatalyst for C-H Borylation of Aromatics and Heteroaromatics
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A newly developed robust catalyst [Ir(COD)(Phen)Cl] (A) was used for the C-H borylation of three dozen aromatics and heteroaromatics with excellent yield and selectivity. Activation of the catalyst was identified by the use of catalytic amounts of water, alcohols, etc., when B2pin2 was used in noncoordinating solvents, while for THF catalytic use of HBpin was required. The results were on par with the in situ based expensive system [Ir(OMe)(COD)]2/dtbbpy or Me4Phen.
- Slack, Eric D.,Colacot, Thomas J.
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supporting information
p. 1561 - 1565
(2021/02/20)
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- Two Ligands Transfer from Ag to Pd: En Route to (SIPr)Pd(CF2H)(X) and Its Application in One-Pot C-H Borylation/Difluoromethylation
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A process for the concurrent transfer of both the NHC ligand and the difluoromethyl group from [(SIPr)Ag(CF2H)] to PdX2 (X = Cl, OAc, and OPiv) for the preparation of [(SIPr)Pd(CF2H)X] complexes is described. These complexes were air-stable and easily underwent transmetalation with aryl pinacol boronate/reductive elimination to generate ArCF2H in high yields. Based on this discovery, the first one-pot C-H borylation and difluoromethylation process for the preparation of difluoromethylated (hetero)arenes was developed.
- Herbert, Simon,Kinzel, Tom,Shen, Qilong,Zhang, Wei,Zhao, Haiwei
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p. 3596 - 3604
(2020/03/23)
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- Highly Selective and Divergent Acyl and Aryl Cross-Couplings of Amides via Ir-Catalyzed C-H Borylation/N-C(O) Activation
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Herein, we demonstrate that amides can be readily coupled with nonactivated arenes via sequential Ir-catalyzed C-H borylation/N-C(O) activation. This methodology provides facile access to biaryl ketones and biaryls by the sterically controlled Ir-catalyzed C-H borylation and divergent acyl and decarbonylative amide N-C(O) and C-C activation. The methodology diverts the traditional acylation and arylation regioselectivity, allowing us to directly utilize readily available arenes and amides to produce valuable ketone and biaryl motifs.
- Gao, Pengcheng,Szostak, Michal
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supporting information
p. 6010 - 6015
(2020/07/30)
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- COMPOSITIONS AND METHODS FOR SELECTIVE SEPARATION OF HYDROCARBON ISOMERS
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The present invention relates to novel metal-organic frameworks (MOFs) comprising tetratopic linkers with small pore apertures. The present invention further relates to methods of utilizing the MOFs of the invention to separate hydrocarbons through adsorptive processes. The present invention further relates to the discovery that Ca(H2tcpb) metal-organic framework (MOF) is capable of separating hydrocarbon isomers from one another through absorptive processes. In one aspect, the invention provides a method of separating C5-C8 hydrocarbon isomers, such that straight chain, mono-branched, and/or multi-branched isomers are each separated from one another. In certain embodiments, this separation is achieved by taking advantage of the temperature dependent adsorptive properties of Ca(H2tcpb) MOF.
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- NNB-type tridentate boryl ligands enabling a highly active iridium catalyst for C–H borylation
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Boryl ligands play a very important role in catalysis because of their very high electron-donating property. In this paper, NNB-type boryl anions were designed as tridentate ligands to promote aryl C–H borylation. In combination with [IrCl(COD)]2/su
- Ding, Siyi,Wang, Linghua,Miao, Zongcheng,Li, Pengfei
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- Sterically controlled C-H/C-H homocoupling of arenes: Via C-H borylation
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A mild one-pot protocol for the synthesis of symmetrical biaryls by sequential Ir-catalyzed C-H borylation and Cu-catalyzed homocoupling of arenes is described. The regiochemistry of the biaryl formed is sterically controlled as dictated by the C-H borylation step. The methodology is also successfully extended to heteroarenes. Some of the products obtained by this approach are impossible to obtain via the Ullmann or the Suzuki coupling protocols. Finally, we have shown a one-pot sequence describing C-H borylation/Cu-catalyzed homocoupling/Pd-catalyzed Suzuki coupling to obtain π-extended arene frameworks.
- Pei, Xiaocong,Zhou, Guan,Li, Xuejing,Xu, Yuchen,Panicker, Resmi C.,Srinivasan, Rajavel
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supporting information
p. 5703 - 5707
(2019/06/19)
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- A novel methoxy-decorated metal-organic framework exhibiting high acetylene and carbon dioxide storage capacities
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A methoxy-decorated novel metal-organic framework (MOF), Cu2(DTPD) (ZJU-12, H4DTPD = 5,5′-(2,6-dimethoxynaphthalene-1,5-diyl)diisophthalic acid) with optimized pore space and open metal sites, was solvothermally synthesized and structurally characterized. The activated ZJU-12a displays a moderately high BET (Brunauer-Emmett-Teller) surface area of 2316 m2 g?1. Due to the pore size of the crystal being consistent with the molecular size and kinetic diameters of C2H2 and CO2, ZJU-12a exhibits a high C2H2 storage capacity of 244 cm3 g?1 and CO2 capture capacity of 134 cm3 g?1 at room temperature.
- Duan, Xing,Cui, Yuanjing,Yang, Yu,Qian, Guodong
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p. 1464 - 1469
(2017/03/17)
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- A New Microporous Metal-Organic Framework for Highly Selective C2H2/CH4 and C2H2/CO2 Separation at Room Temperature
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We have successfully designed and synthesized a new tetracarboxylic linker, which constructed its first three-dimensional microporous metal-organic framework (MOF), [Cu2(DDPD)(H2O)2]?Gx (ZJU-13, H4DDPD=5,5'-(2,6-dihydroxynaphthalene-1,5-diyl)diisophthalic acid, ZJU=Zhejiang University, G = guest molecules) via solvothermal reaction. Due to open Cu2+ sites and optimized pore size, the activated ZJU-13a displays high separation selectivity for C2H2/CH4 of 74 and C2H2/CO2 of 12.5 at low pressure by using Ideal Adsorbed Solution Theory (IAST) simulation at room temperature.
- Duan, Xing,Xia, Tifeng,Ji, Zhenguo,Cui, Yuanjing,Yang, Yu,Qian, Guodong
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supporting information
p. 1289 - 1293
(2017/09/02)
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- Preparation method of novel 5-[4-(1-carboxyl naphthyl)]-isophthalic acid
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The invention discloses a preparation method of novel 5-[4-(1-carboxyl naphthyl)]-isophthalic acid. 4-naphthoic acid is subjected to a methyl esterification reaction to generate a compound A 4-bromo-naphthoic acid methyl ester; 5-amino-dimethyl isophthalate is subjected to a diazotization bromination reaction to generate a compound B 5-bromo-dimethyl isophthalate; under the nitrogen protection condition, 5-bromo-dimethyl isophthalate and bis(pinacolato)diboron are subjected to a Miyaura boric acid esterification reaction by adding a catalyst to generate a compound C 3,5-dimethoxycarbonyl phenylboronic acid pinacol ester; the compound A and the compound C are subjected to a nitrogen protection reaction under the action of a catalyst to generate a compound D 5-[4-(1-methoxycarbonyl naphthyl)]-dimethyl isophthalate; the target compound E 5-[4-(1-carboxyl naphthyl)]-isophthalic acid is generated through a hydrolysis reaction, wherein the target compound E is shown as the following formula (please see the formula in the description). The method has the advantages of being simple in synthesizing method, low in synthesizing cost, and high in yield and product purity.
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Paragraph 0023; 0024
(2016/10/20)
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- Novel synthesis method for 5-[10-(9-carbosyl anthryl)]-isophthalic acid
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The invention provides a novel synthesis method for 5-[10-(9-carbosyl anthryl)]-isophthalic acid. A diazotization bromination reaction is conducted on 5-amino-1,3-benzenedicarboxylic acid dimethyl ester to synthesize a compound A, namely, 5-bromine-1,3-benzenedicarboxylic acid dimethyl ester, and catalysts are added to 5-bromine-1,3-benzenedicarboxylic acid dimethyl ester under the condition of nitrogen protection to make 5-bromine-1,3-benzenedicarboxylic acid dimethyl ester react with bis(pinacolato)diboron so as to generate a compound B, namely, 3,5-bis(methoxycarbonylethyl)phenylboronic acid pinacol ester. In addition, anthracene-9-carboxylic acid is bromized to obtain a compound C, namely, 10-bromine-9-carboxylic acid, the compound C is subjected to methyl esterification to generate a compound D, namely, 10-bromine-9-anthracene methyl formate, and the compound D and the compound B are subjected to a nitrogen protection reaction under the effect of catalysts to generate a compound E, namely, 5-[10-(9-methoxycarbonyl group anthryl)]-benzenedicarboxylic acid dimethyl ester, and a target compound F, namely, 5-[10-(9-carboxyl anthryl)]-isophthalic acid through a hydrolysis reaction. The target compound F is shown in the figure.
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Paragraph 0021
(2017/03/08)
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- A NbO-type metal-organic framework exhibiting high deliverable capacity for methane storage
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A copper-based NbO-type metal-organic framework ZJNU-50 constructed from a tetracarboxylate incorporating phenylethyne as a spacer exhibited an exceptionally high methane working capacity of 184 cm3 (STP) cm-3 for methane storage. The value is among the highest reported for MOF materials. This journal is
- Song, Chengling,Ling, Yajing,Feng, Yunlong,Zhou, Wei,Yildirim, Taner,He, Yabing
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p. 8508 - 8511
(2015/05/20)
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- Novel microporous metal-organic framework exhibiting high acetylene and methane storage capacities
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A new organic hexacarboxylic acid, 5,5′,5″-(9H-carbazole-3,6,9-triyl)triisophthalic acid (H6CTIA), was developed to construct its first microporous metal-organic framework (MOF), Cu6(CTIA)2 (ZJU-70). With open metal sites and suitable pore sizes, this MOF exhibits high acetylene and methane storage capacities at room temperature.
- Duan, Xing,Wu, Chuande,Xiang, Shengchang,Zhou, Wei,Yildirim, Taner,Cui, Yuanjing,Yang, Yu,Chen, Banglin,Qian, Guodong
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p. 4377 - 4381
(2015/05/20)
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- Double N,B-Type Bidentate Boryl Ligands Enabling a Highly Active Iridium Catalyst for C-H Borylation
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Boryl ligands hold promise in catalysis due to their very high electron-donating property. In this communication double N,B-type boryl anions were designed as bidentate ligands to promote an sp2 C-H borylation reaction. A symmetric pyridine-con
- Wang, Guanghui,Xu, Liang,Li, Pengfei
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supporting information
p. 8058 - 8061
(2015/07/15)
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- Regioselective conversion of arenes to N-aryl-1,2,3-triazoles Using C-H Borylation
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A one-pot protocol for the synthesis of N-aryl 1,2,3-triazoles from arenes by an iridium-catalyzed C-H borylation/copper catalyzed azidation/click sequence is described. 1mol % of Cu(OTf)2 was found to efficiently catalyze both the azidation and the click reaction. The applicability of this method is demonstrated by the late-stage chemoselective installation of 1,2,3-triazole moiety into unactivated molecules of pharmaceutical importance.
- Srinivasan, Rajavel,Coyne, Anthony G.,Abell, Chris
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supporting information
p. 11680 - 11684
(2014/10/15)
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- Synthesis of pinacol arylboronates from aromatic amines: A metal-free transformation
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A metal-free borylation process based on Sandmeyer-type transformation using arylamines derivatives as the substrates has been developed. Through optimization of the reaction conditions, this novel conversion can be successfully applied to a wide range of aromatic amines, affording borylation products in moderate to good yields. Various functionalized arylboronates, which are difficult to access by other methods, can be easily obtained with this metal-free transformation. Moreover, this transformation can be followed by Suzuki-Miyaura cross-coupling without purification of the borylation products, which enhances the practical usefulness of this method. A possible reaction mechanism involving radical species has been proposed.
- Qiu, Di,Jin, Liang,Zheng, Zhitong,Meng, He,Mo, Fanyang,Wang, Xi,Zhang, Yan,Wang, Jianbo
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p. 1923 - 1933
(2013/03/29)
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- Methane storage in metal-organic frameworks: Current records, surprise findings, and challenges
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We have examined the methane uptake properties of six of the most promising metal organic framework (MOF) materials: PCN-14, UTSA-20, HKUST-1, Ni-MOF-74 (Ni-CPO-27), NU-111, and NU-125. We discovered that HKUST-1, a material that is commercially available in gram scale, exhibits a room-temperature volumetric methane uptake that exceeds any value reported to date. The total uptake is about 230 cc(STP)/cc at 35 bar and 270 cc(STP)/cc at 65 bar, which meets the new volumetric target recently set by the Department of Energy (DOE) if the packing efficiency loss is ignored. We emphasize that MOFs with high surface areas and pore volumes perform better overall. NU-111, for example, reaches ～75% of both the gravimetric and the volumetric targets. We find that values for gravimetric uptake, pore volume, and inverse density of the MOFs we studied scale essentially linearly with surface area. From this linear dependence, we estimate that a MOF with surface area 7500 m2/g and pore volume 3.2 cc/g could reach the current DOE gravimetric target of 0.5 g/g while simultaneously exhibiting around ～200 cc/cc volumetric uptake. We note that while values for volumetric uptake are based on ideal single crystal densities, in reality the packing densities of MOFs are much lower. Finally, we show that compacting HKUST-1 into wafer shapes partially collapses the framework, decreasing both volumetric and gravimetric uptake significantly. Hence, one of the important challenges going forward is to find ways to pack MOFs efficiently without serious damage or to synthesize MOFs that can withstand substantial mechanical pressure.
- Peng, Yang,Krungleviciute, Vaiva,Eryazici, Ibrahim,Hupp, Joseph T.,Farha, Omar K.,Yildirim, Taner
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supporting information
p. 11887 - 11894
(2013/09/02)
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- A microporous metal-organic framework of a rare sty topology for high CH4 storage at room temperature
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A rare sty type microporous metal-organic framework, Cu2(FDDI) (ZJU-25; H4FDDI = tetramethyl 5,5′-(9H-fluorene-2,7-diyl) diisophthalate acid), was solvothermally synthesized and structurally characterized. With open metal sites and suitable pore space for their interactions with methane molecules, ZJU-25a exhibits absolute methane storage of 180 cm3(STP) cm-3 at room temperature and 35 bar, enabling it to be one of the very few porous MOFs whose methane storage capacities have met and/or approached the DOE target of 180 cm3(STP) cm-3 for material-based methane storage. The Royal Society of Chemistry 2013.
- Duan, Xing,Yu, Jiancan,Cai, Jianfeng,He, Yabing,Wu, Chuande,Zhou, Wei,Yildirim, Taner,Zhang, Zhangjing,Xiang, Shengchang,O'Keeffe, Michael,Chen, Banglin,Qian, Guodong
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supporting information
p. 2043 - 2045
(2013/03/28)
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- Removal of toxic dyes from aqueous medium using adenine based bicomponent hydrogel
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By utilizing hydrogen bonding and π-π stacking interactions, we have demonstrated the construction of three dimensional adenine based gel networks due to the self assembly with complementary tricarboxylic acid derivatives which were designed and unambiguously characterized with the help of NMR, HRMS, and FTIR. Upon cooling the homogeneous aqueous solution of adenine and tricarboxylic acid, it formed hydrogels which were thermoreversible in nature and characterized by various instrumental techniques such as OM, FESEM, TEM, AFM, FL, XRD, FT-IR, rheology etc. Networks of belts in the hydrogel were clearly observed and the dimension of belt depended on the tricarboxylic acid used. The intermolecular hydrogen bonds which were considered to be the driving force for the formation of stable gel were confirmed by FT-IR studies. In spite of the absence of symmetry either in bpca or adenine, these two moieties surprisingly produced gels and it was due to the symmetrical position of complementary interaction sites between adenine and tricarboxylic acids. The mechanical strength of the hydrogel network as revealed by rheological study depended on the tricarboxylic acid used in the two-component systems and also on the composition of fixed pair. These kind of hydrogels have potential to be utilized as inexpensive materials for the treatment of waste water containing organic dyes (methylene blue, rhodamine 6G and crystal violet) that are widely used in textile as well as dye industries.
- Sukul, Pradip K.,Malik, Sudip
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p. 1902 - 1915
(2013/03/13)
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- An accessible bicyclic architecture for synthetic lectins
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Bicyclic carbohydrate receptors are easier to synthesise than tri- or tetra-cyclic relatives, and are better adapted to bind monosaccharide residues with bulky appendages. Disaccharides containing β-glucosyl units are preferred substrates.
- Howgego, Joshua D.,Butts, Craig P.,Crump, Matthew P.,Davis, Anthony P.
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supporting information
p. 3110 - 3112
(2013/06/27)
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- A general strategy for the perfluoroalkylation of arenes and arylbromides by using arylboronate esters and [(phen)CuRF]
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A versatile method for the synthesis of aryl perfluoroalkanes from arenes and aryl bromides is described. Substituted arenes or aryl bromides are converted in situ to an aryl boronate ester that readily undergoes perfluoroalkylation in air with [(phen)CuRF]. A broad range of aryl bromide substrates were perfluoroalkylated in good yield for the first time. [(phen)CuCF3] is now commercially available and has been prepared on 20g scale. Copyright
- Litvinas, Nichole D.,Fier, Patrick S.,Hartwig, John F.
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supporting information; experimental part
p. 536 - 539
(2012/02/16)
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- Highly selective trifluoromethylation of 1,3-disubstituted arenes through iridium-catalyzed arene borylation
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The old one two: A sequential iridium-catalyzed borylation and copper-catalyzed trifluoromethylation of arenes is described (see scheme; Pin=pinacol). The reaction is conducted under mild reaction conditions and tolerates a variety of functional groups. T
- Liu, Tianfei,Shao, Xinxin,Wu, Yaming,Shen, Qilong
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supporting information; experimental part
p. 540 - 543
(2012/03/11)
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- Novel metal-organic framework based on cubic and trisoctahedral supermolecular building blocks: Topological analysis and photoluminescent property
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A novel supermolecular building blocks (SBBs) based metal-organic framework (MOF), with formula [Zn7(TMBHB)2?2NO 3?5DMF?4CH3CH2OH?6H 2O]n (SDU-1), was constructed from C3/s
- Zhao, Xiaoliang,Wang, Xiaoyang,Wang, Suna,Dou, Jianmin,Cui, Peipei,Chen, Zhen,Sun, Di,Wang, Xingpo,Sun, Daofeng
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scheme or table
p. 2736 - 2739
(2012/08/14)
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- Introduction of functionalized mesopores to metal-organic frameworks via metal-ligand-fragment coassembly
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Introduction of functionalized mesopores into microporous metal-organic frameworks (MOFs) can endow them with suitable properties for applications in gas storage, separation, catalysis, and drug delivery. However, common methods for functionalization (inc
- Park, Jinhee,Wang, Zhiyong U.,Sun, Lin-Bing,Chen, Ying-Pin,Zhou, Hong-Cai
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p. 20110 - 20116
(2013/02/23)
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- Efficient monophosphorus ligands for palladium-catalyzed miyaura borylation
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In combination with the Bedford Pd precursor, the new biaryl monophosphorus ligand 5 was efficient for palladium-catalyzed Miyaura borylation of sterically hindered aryl bromides at low catalyst loadings.
- Tang, Wenjun,Keshipeddy, Santosh,Zhang, Yongda,Wei, Xudong,Savoie, Jolaine,Patel, Nitinchandra D.,Yee, Nathan K.,Senanayake, Chris H.
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scheme or table
p. 1366 - 1369
(2011/05/15)
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- Design, synthesis and photoactivation studies of fluorous photolabels
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Two fluorous diazirine photolabels were designed, synthesized and subjected to photoactivation studies. The photoactivation studies revealed an unexpected photoreaction when the fluorous tag was directly connected to the diazirine ring, leading to the formation of a fluorous alkene. The more efficient photolabel of the two was identified as a flexible precursor for target specific photoaffinity labels for fluorous proteomics by adding appropriate ligands depending on the target protein subset. As a proof of feasibility, mannose residues were added to the photolabel making it a potential photoaffinity label to tag proteins that bind mannose.
- Babu Kumar, Arun,Anderson, Jordan Micheal,Manetsch, Roman
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p. 6284 - 6292
(2011/10/10)
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- (3-oxo)pyridazin-4-ylurea derivatives as PDE4 inhibitors
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New (3-oxo)pyridazin-4-ylurea derivatives having the chemcial structure of formula (I) are disclosed; as well as process for their preparation, pharmaceutical compositions comprising them and their use in therapy as inhibitors of the phosphodiesterase IV (PDE4).
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Page/Page column 59
(2010/07/03)
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- Anti-infective agents
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The present invention relates to the use of molecules having a spacer unit, linker and recognition unit(s) for the treatment and prevention of various diseases, disorders and conditions. In particular, the present invention provides compounds useful in pr
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- Synthesis and photophysical characterization of porphyrin, chlorin and bacteriochlorin molecules bearing tethers for surface attachment
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The ability to tailor synthetic porphyrin, chlorin and bacteriochlorin molecules holds promise for diverse studies in artificial photosynthesis. Toward this goal, the synthesis and photophysical characterization of five tetrapyrrole compounds is described
- Muthiah, Chinnasamy,Taniguchi, Masahiko,Kim, Han-Je,Schmidt, Izabela,Kee, Hooi Ling,Holten, Dewey,Bocian, David F.,Lindsey, Jonathan S.
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p. 1513 - 1528
(2008/09/18)
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- Mimicking the binding motifs found in the crystal structures of protein-carbohydrate complexes: An aromatic analogue of serine or threonine side chain hydroxyl/main chain amide
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An aromatic analogue of the side chain hydroxyl/main chain amide of Ser or Thr was used for the construction of artificial receptors for N-acetylneuraminic acid (Neu5Ac), the most common occurring sialic acid. The acyclic receptors, incorporating only neu
- Mazik, Monika,Koenig, Alexander
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p. 3271 - 3276
(2008/02/10)
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- Recognition properties of an acyclic biphenyl-based receptor toward carbohydrates
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(Figure Presented) Biphenyl-based receptor 1, incorporating four heterocyclic recognition units, was synthesized, and its binding properties toward neutral sugars were determined. Receptor 1 is a representative of a new series of acyclic carbohydrate-bind
- Mazik, Monika,Koenig, Alexander
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p. 7854 - 7857
(2007/10/03)
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