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Fmoc-based synthesis of glycolate ester peptides for the assembly of de novo designed multimeric proteins using subtiligase
An automated method utilizing Fmoc-protected amino acids has been developed for the synthesis of glycolate ester peptides as substrates for subtiligase. As a test of this methodology, peptide esters containing α-helical sequences that specify the association into 3- and 4-helix bundles were synthesized, and used to explore the suitability of subtiligase as a tool, for the generation of covalently linked bundles. The feasibility of creating de novo designed, single-chain or cyclic structures from simple, readily-synthesized modules has been demonstrated.
Suich, Daniel J.,Ballinger, Marcus D.,Wells, James A.,DeGrado, William F.
p. 6653 - 6656
(1996)
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1,5-Disubstituted 1,2,3-Triazoles as Amide Bond Isosteres Yield Novel Tumor-Targeting Minigastrin Analogs
1,5-Disubstituted 1,2,3-triazoles (1,5-Tz) are considered bioisosteres of cis-amide bonds. However, their use for enhancing the pharmacological properties of peptides or proteins is not yet well established. Aiming to illustrate their utility, we chose the peptide conjugate [Nle15]MG11 (DOTA-dGlu-Ala-Tyr-Gly-Trp-Nle-Asp-Phe-NH2) as a model compound since it is known that the cholecystokinin-2 receptor (CCK2R) is able to accommodate turn conformations. Analogs of [Nle15]MG11 incorporating 1,5-Tz in the backbone were synthesized and radiolabeled with lutetium-177, and their pharmacological properties (cell internalization, receptor binding affinity and specificity, plasma stability, and biodistribution) were evaluated and compared with [Nle15]MG11 as well as their previously reported analogs bearing 1,4-disubstituted 1,2,3-triazoles. Our investigations led to the discovery of novel triazole-modified analogs of [Nle15]MG11 with nanomolar CCK2R-binding affinity and 2-fold increased tumor uptake. This study illustrates that substitution of amides by 1,5-disubstituted 1,2,3-triazoles is an effective strategy to enhance the pharmacological properties of biologically active peptides.
Grob, Nathalie M.,Schibli, Roger,Béhé, Martin,Valverde, Ibai E.,Mindt, Thomas L.
supporting information
p. 585 - 592
(2021/04/12)

Engineering Dirhodium Artificial Metalloenzymes for Diazo Coupling Cascade Reactions**
Artificial metalloenzymes (ArMs) are commonly used to control the stereoselectivity of catalytic reactions, but controlling chemoselectivity remains challenging. In this study, we engineer a dirhodium ArM to catalyze diazo cross-coupling to form an alkene that, in a one-pot cascade reaction, is reduced to an alkane with high enantioselectivity (typically >99 % ee) by an alkene reductase. The numerous protein and small molecule components required for the cascade reaction had minimal effect on ArM catalysis. Directed evolution of the ArM led to improved yields and E/Z selectivities for a variety of substrates, which translated to cascade reaction yields. MD simulations of ArM variants were used to understand the structural role of the cofactor on ArM conformational dynamics. These results highlight the ability of ArMs to control both catalyst stereoselectivity and chemoselectivity to enable reactions in complex media that would otherwise lead to undesired side reactions.
Bultman, Max J.,Huang, Rui,Lewis, Jared C.,Li, Ying,Roux, Benoit,Upp, David M.
supporting information
p. 23672 - 23677
(2021/08/23)

Visible-Light-Induced Oxidative α-Alkylation of Glycine Derivatives with Ethers under Metal-Free Conditions
In this work, a visible-light-induced oxidative α-alkylation of glycine derivatives with ethers has been developed in the presence of catalytic Eosin Y. Under the blue light of a 3 W LED, a range of α-etherized glycine derivatives, including α-amino esters, α-amino ketones and α-amino amides, were achieved with good to excellent yields and functional group tolerance with tert-butyl hydroperoxide (TBHP) as oxidant at ambient temperature. The operationally easy procedure provides an economical, metal-free, and mild alternative for the synthesis of the α-etherized glycine derivatives.
Song, Yang,Zhang, Hao,Guo, Jiabao,Shao, Yifei,Ding, Yuzhou,Zhu, Li,Yao, Xiaoquan
p. 5914 - 5921
(2021/11/22)

Visible-Light-Assisted Gold-Catalyzed Fluoroarylation of Allenoates
A strategically novel synthetic method for the fluoroarylation of allenic ester was developed that enables the expedient construction of a host of β-fluoroalkyl-containing cinnamate derivatives. The reaction proceeds through visible-light-promoted gold redox catalysis, occurs smoothly under very mild reaction conditions, accommodates a large variety of functional groups, and more importantly allows the incorporation of fluorine and aryl groups with excellent regio- and stereoselectivity. The concomitant activation mode for both the allene motif and the hydrogen fluoride is key for the success of the reaction.
Feng, Chao,Tang, Hai-Jun,Zhang, Xinggui,Zhang, Yu-Feng
supporting information
p. 5242 - 5247
(2020/02/28)

E- and chemoselective thia-Michael addition to benzyl allenoate
Different thiols were successfully reacted with benzyl allenoate resulting in E-selective thia-Michael addition product with α,β-unsaturation as confirmed by single crystal x-ray crystallographic analysis. The thia-Michael addition is chemoselective and free amine and alcohol groups were well tolerated. Catalytic triethylamine was required for high conversion. Fair to excellent yields were obtained for a variety of aliphatic, aryl and heteroaryl thiols.
Bibi, Rifhat,Murtaza, Amna,Khan, Khalid Mohammed,Rehman, Zia ur,Saeed, Aamer,Tahir, Muhammad Nawaz,Hassan, Abbas
supporting information
p. 969 - 975
(2020/08/05)

Synthesis, antiinflammatory activity, and molecular docking studies of bisphosphonic esters as potential MMP-8 and MMP-9 inhibitors
Bisphosphonic acids (or bisphosphonates) have been successfully used in the clinic treatment of bone diseases for over decades. Additionally, the antiinflammatory activity of these compounds has been gaining attention. In our previous work, we synthesized and in vivo evaluated the bisphosphonic esters 1 and 2, finding a moderate edema inhibition upon oral and topical administration on BALB/c mice. Thus, in this work, the bioisosteric replacement of an amide functional group for an ester afforded the new bisphosphonates 3–6, which had a moderate oral edema inhibition (25 mg/kg dose) and a significant topical antiinflammatory activity (2 mg/ear) on BALB/c mice, with 6 being the most active hit (55.9% edema inhibition), comparable to the positive control (55.5% edema inhibition) on a TPA topical model. Next, to assess the acute toxicity of the synthesized derivatives, test animals were administered with 50–100 mg/kg of 3–6, respectively, by an oral route, and after 14 days, neither lethality nor a significative weight loss were observed. Finally, a structure–activity relationship (SAR) and a molecular docking analysis of 3–6 helped us to explain the trend observed in biological tests. Considering all these aspects, we propose the inhibition of MMP-8 and MMP-9 as a possible action mechanism of the synthesized derivatives.
Cortes-Pacheco, Abimelek,Jiménez-Arellanes, María Adelina,Juárez-Vázquez, María del Carmen,López-Torres, Adolfo,Palacios-Can, Francisco José,Ramírez-Marroquín, Oscar Abelardo,Razo-Hernández, Rodrigo Said,Valcarcel-Gami?o, José Antonio
supporting information
p. 1277 - 1287
(2020/07/10)

Cross coupling of sulfonyl radicals with silver-based carbenes: A simple approach to β-carbonyl arylsulfones
A coupling reaction between sulfonyl radicals and silver-based carbenes has been well established. This simple radical-carbene coupling (RCC) process provided an efficient approach to a variety of β-carbonyl arylsulfones from sodium arylsulfinates and diazo compounds, and was characterized by wide substrate scope, easy scale-up, simple manipulation, accessible starting materials, and mild reaction conditions.
Li, Jingjing,Lian, Pengcheng,Wan, Xiaobing,Wang, Hanghang,Zheng, Yonggao
supporting information
p. 2163 - 2169
(2020/03/27)

Enantioselective Allenoate-Claisen Rearrangement Using Chiral Phosphate Catalysts
Herein we report the first highly enantioselective allenoate-Claisen rearrangement using doubly axially chiral phosphate sodium salts as catalysts. This synthetic method provides access to β-amino acid derivatives with vicinal stereocenters in up to 95percent ee. We also investigated the mechanism of enantioinduction by transition state (TS) computations with DFT as well as statistical modeling of the relationship between selectivity and the molecular features of both the catalyst and substrate. The mutual interactions of charge-separated regions in both the zwitterionic intermediate generated by reaction of an amine to the allenoate and the Na+-salt of the chiral phosphate leads to an orientation of the TS in the catalytic pocket that maximizes favorable noncovalent interactions. Crucial arene-arene interactions at the periphery of the catalyst lead to a differentiation of the TS diastereomers. These interactions were interrogated using DFT calculations and validated through statistical modeling of parameters describing noncovalent interactions.
Ellwart, Mario,Gensch, Tobias,Han, Seo-Jung,Lin, Hsin-Hui,Miró, Javier,Sigman, Matthew S.,Toste, F. Dean
supporting information
p. 6390 - 6399
(2020/04/27)

SULFOXIDE-BASED REAGENT FOR MASS SPECTROMETRY
The present invention relates to sulfoxide-based reagents suitable in the mass spectrometric determination of analyte molecules such as peptides as well as adducts of such reagents and analyte molecules and applications of said reagents and adducts. Further, the present invention relates to methods for the mass spectrometric determination of analyte molecules.
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(2019/04/09)

Sulfinate-Engaged Nucleophilic Addition Induced Allylic Alkylation of Allenoates
A strategically novel Pd-catalyzed nucleophilic addition induced allylic alkylation reaction (NAAA) of allenoates has been successfully accomplished. By judiciously integrating ZnCl2-promoted Michael addition with Pd-catalyzed allylic alkylation, allenoates readily undergo allyl-sunfonylation at the internal double bond, thus providing a straightforward avenue for the rapid assembly of a host of structurally diversified α-allyl-β-sufonylbut-3-enoate derivatives. The success of this transformation profits from a delicate control of the reaction kinetic of each elementary step, thanks to the synergistic interaction of Pd/Zn bimetallic system, thus suppressing either direct allylic sulfonylation or premature quenching of therein in situ generated ester enolate intermediate. Furthermore, by expanding the scope of workable Michael acceptor beyond those previously required doubly activated ones, such as methylenemalononitrile, the present work substantially enriches the repertoire of NAAA reactions.
Lin, Ling-Zhi,Che, Yuan-Yuan,Bai, Peng-Bo,Feng, Chao
supporting information
p. 7424 - 7429
(2019/10/02)

Virtual Screening Identifies Irreversible FMS-like Tyrosine Kinase 3 Inhibitors with Activity toward Resistance-Conferring Mutations
The use of covalent irreversible binding inhibitors is an established concept for drug development. Usually, the discovery of new irreversible kinase inhibitors occurs serendipitously, showing that efficient rational approaches for the rapid discovery of new drugs are needed. Herein, we report a virtual screening strategy that led to the discovery of irreversible inhibitors of FMS-like tyrosine kinase 3 (FLT3) involved in the pathogenesis of acute myeloid leukemia. A virtual screening library was designed to target the highly conserved Cys828 residue preceding the DFG motif by modification of reported reversible inhibitors with chemically reactive groups. Prospective covalent docking allowed the identification of two lead series, resulting in a massive increase in inhibition of kinase activity and cell viability by irreversible inhibitors compared to the corresponding reversible scaffolds. Lead compound 4b (BSc5371) displays superior cytotoxicity in FLT3-dependent cell lines to compounds in recent clinical trials and overcomes drug-resistant mutations.
Bensinger, Dennis,Stubba, Daniel,Cremer, Anjali,Kohl, Vanessa,Wa?mer, Theresa,Stuckert, Johanna,Engemann, Victoria,Stegmaier, Kimberly,Schmitz, Katja,Schmidt, Boris
supporting information
p. 2428 - 2446
(2019/03/11)

A General Catalytic Route to Enantioenriched Isoindolinones and Phthalides: Application in the Synthesis of (S)-PD 172938
Chiral Br?nsted acid catalyzed enantioselective syntheses of isoindolinones and phthalides have been accomplished via tandem Mannich-lactamization and aldol-lactonization reactions, respectively. A variety of enantioenriched isoindolinones (up to 99% ee) and phthalides (up to 85% ee) containing α-diazoesters were afforded in excellent yields. Furthermore, a concise synthesis of (S)-PD 172938 has been demonstrated by using this protocol.
Ray, Sumit K.,Sadhu, Milon M.,Biswas, Rayhan G.,Unhale, Rajshekhar A.,Singh, Vinod K.
supporting information

(2019/01/21)

A General Catalytic Route to Enantioenriched Isoindolinones and Phthalides: Application in the Synthesis of (S)-PD 172938
Chiral Br?nsted acid catalyzed enantioselective syntheses of isoindolinones and phthalides have been accomplished via tandem Mannich-lactamization and aldol-lactonization reactions, respectively. A variety of enantioenriched isoindolinones (up to 99% ee) and phthalides (up to 85% ee) containing α-diazoesters were afforded in excellent yields. Furthermore, a concise synthesis of (S)-PD 172938 has been demonstrated by using this protocol.
Ray, Sumit K.,Sadhu, Milon M.,Biswas, Rayhan G.,Unhale, Rajshekhar A.,Singh, Vinod K.
supporting information
p. 417 - 422
(2019/01/23)

Two Distinct Ag(I)- And Au(I)-Catalyzed Olefinations between α-Diazo Esters and N-Boc-Derived Imines
Metal-catalyzed reactions between α-diazo esters and imines were well-known to yield aziridine derivatives exclusively. This work reports two new olefination reactions between N-Boc-derived (Boc = tert-Butyloxycarbonyl) imines and α-diazo esters with Ag(I) and Au(I) catalysts, respectively. Our mechanistic studies reveal that these new olefinations involve an initial attack of diazo esters on metal/imine complexes to form Mannich-addition intermediates, which subsequently afford α-aryl-β-aminoacrylates via a Roskamp reaction, or to form β-aryl-β-aminoacrylates via the formation of silver carbenes.
Kardile, Rahul Dadabhau,Liu, Rai-Shung
supporting information
p. 6452 - 6456
(2019/09/06)

A Sulfoxide-Based Isobaric Labelling Reagent for Accurate Quantitative Mass Spectrometry
Modern proteomics requires reagents for exact quantification of peptides in complex mixtures. Peptide labelling is most typically achieved with isobaric tags that consist of a balancer and a reporter part that separate in the gas phase. An ingenious distribution of stable isotopes provides multiple reagents with identical molecular weight but a different mass of the reporter groups, allowing relative quantification of multiple samples in one measurement. Here we report a new isobaric labelling reagent, where the balancer and the reporter are linked by a sulfoxide group, which, based on the sulfoxide pyrolysis, leads to easy and asymmetric cleavage at low fragmentation energy. The fragmentation of our new design is significantly improved, yielding more intense complementary ion signals, allowing complementary ion cluster analysis as well.
Stadlmeier, Michael,Bogena, Jana,Wallner, Miriam,Wühr, Martin,Carell, Thomas
supporting information
p. 2958 - 2962
(2018/02/21)

Convenient synthesis, antimalarial and antimicrobial potential of thioethereal 1,4-disubstituted 1,2,3-triazoles with ester functionality
This paper elicits the synthesis of twenty five 1,4-disubstituted 1,2,3-triazole analogs (5a–5y) comprising thioether and ester linkages from aryl(prop-2-yn-1-yl)sulfanes and benzyl 2-azidoacetates employing Cu(I) catalyzed Huisgen 1,3-dipolar cycloaddition. Structures of synthesized compounds were elucidated by spectroscopic techniques like FTIR, 1H NMR, 13C NMR, and HRMS. Newly synthesized compounds were screened for in vitro antimalarial evaluation against P. falciparum strain and microbicidal potential against B. subtilis, S. epidermidis, E. coli, P. aeruginosa, C. albicans, and A. niger. Some of synthesized triazoles displayed moderate antimalarial activity against tested strain, while, the compounds 5i and 5n were found to exhibit significant inhibitory activity against most of the tested microbial strains.
Kaushik,Pahwa, Ashima
p. 458 - 469
(2017/10/13)

A Tunable Route to Prepare α,β-Unsaturated Esters and α,β-Unsaturated-γ-Keto Esters through Copper-Catalyzed Coupling of Alkenyl Boronic Acids with Phosphorus Ylides
A tunable strategy to prepare α,β-unsaturated esters and α,β-unsaturated-γ-keto esters in good to excellent yields was developed through copper-catalyzed oxidative coupling of phosphorus ylides with alkenyl boronic acids under mild conditions. The reaction without water afforded α,β-unsaturated esters, ketones, and amides while α,β-unsaturated-γ-keto esters, 1,4-α,β-unsaturated diketones and α,β-unsaturated-γ-keto amides were obtained when using 5.0 equiv. of water. H2O18 labeling experiments showed that water played an important role in the formation of α,β-unsaturated-γ-keto esters. A plausible formation mechanism for α,β-unsaturated esters and α,β-unsaturated-γ-keto esters was proposed based on mechanistic studies. Phosphonium salts could also be used directly as coupling partners instead of phosphorus ylides. The reaction exhibited a broad substrate scope, good functional group tolerance, good regioselectivity, and diverse coupling products. (Figure presented.).
Bi, Hong-Yan,Liu, Feng-Ping,Liang, Cui,Su, Gui-Fa,Mo, Dong-Liang
supporting information
p. 1510 - 1516
(2018/03/05)

A chiral Br?nsted acid-catalyzed highly enantioselective Mannich-type reaction of α-diazo esters with in situ generated N -acyl ketimines
A chiral phosphoric acid-catalyzed asymmetric Mannich-type reaction of α-diazo esters with in situ generated N-acyl ketimines, derived from 3-hydroxyisoindolinones has been demonstrated in this communication. A variety of isoindolinone-based α-amino diazo esters bearing a quaternary stereogenic center were afforded in high yields (up to 99%) with excellent enantioselectivities (up to 99% ee). Furthermore, the synthetic utility of the products has been depicted by the hydrogenation of the diazo moiety of adducts.
Unhale, Rajshekhar A.,Sadhu, Milon M.,Ray, Sumit K.,Biswas, Rayhan G.,Singh, Vinod K.
supporting information
p. 3516 - 3519
(2018/04/10)

Interception of Secondary Amide Ylide with Sulfonamides: Catalyst-Controlled Synthesis of N-Sulfonylamidine Derivatives
A novel, secondary amide activation strategy has been developed through the in situ generation of ylides from amides and diazoacetates. Under the developed reaction conditions, Mn-catalyzed ylide formation and interception reaction by sulfonamide delivered a variety of N-sulfonylamidines. Notably, when highly active Zn(OTf)2 was used as the catalyst, further N-H insertion products were obtained. In contrast with traditional methods, our amide activation strategy is distinguished by accessible starting material, inexpensive catalyst, and broad substrate scope.
Chen, Jijun,Long, Wenhao,Yang, Yonggang,Wan, Xiaobing
supporting information
p. 2663 - 2666
(2018/05/22)

In situ generation of nitrile oxides from copper carbene and tert -butyl nitrite: Synthesis of fully substituted isoxazoles
Herein, we present a novel [3 + 2] cycloaddition reaction of β-keto esters with nitrile oxides, which were generated in situ from copper carbene and tert-butyl nitrite. This three-component reaction provides new methodology for the direct synthesis of fully substituted isoxazole derivatives, featuring mild reaction conditions, readily accessible starting materials and simple operation. The experimental studies and DFT calculations suggest that the reaction starts with the generation of the key intermediate nitrile oxides, followed by a [3 + 2] cycloaddition reaction of β-keto esters to give the final isoxazole products.
Chen, Rongxiang,Ogunlana, Abosede Adejoke,Fang, Shangwen,Long, Wenhao,Sun, Hongmei,Bao, Xiaoguang,Wan, Xiaobing
supporting information
p. 4683 - 4687
(2018/07/06)

Synthesis and Antimicrobial Evaluation of (1-(2-(Benzyloxy)-2-oxoethyl)-1H-1,2,3-triazol-4-yl)methyl Benzoate Analogues
A convenient one pot synthesis of 20 (1-(2-(benzyloxy)-2-oxoethyl)-1H-1,2,3-triazol-4-yl)methyl benzoate analogues (5a–5t) with ester functionality was carried out via Cu(I) catalyzed click reaction between prop-2-yn-1-yl benzoates and benzyl 2-azidoacetates. The structure of synthesized triazoles were explicated by various spectral techniques like FT-IR, 1H NMR, 13C NMR, and high-resolution mass spectrometry and evaluated for in vitro antimicrobial potential against Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Enterobacter aerogenes, Candida albicans, and Aspergillus niger. Most of synthesized triazole derivatives exhibited average to excellent activity against tested microbial strains.
Kaushik,Pahwa, Ashima,Kumar, Devinder,Kumar, Ashwani,Singh, Dharmendra,Kumar, Krishan,Luxmi, Raj
p. 1720 - 1728
(2018/07/25)

In Situ Generation of Oxazole Ylide and Interception with Sulfonamide: Construction of Amidines Using Two Diazo Molecules
A novel generation of oxazole ylide and interception with sulfonamide have been well developed to construct fully substituted amidines. This copper-catalyzed four-component reaction incorporates two diazo molecules to target amidines and shows broad substrate scope, excellent functional groups tolerance and good to excellent yields.
Chen, Jijun,Long, Wenhao,Zhao, Yanwei,Li, Haiyan,Zheng, Yonggao,Lian, Pengcheng,Wan, Xiaobing
supporting information
p. 857 - 865
(2018/07/31)

Regio- and Stereoselective Nickel-Catalyzed Coupling of Boronic Acids with Allenoates
The Ni(II)-catalyzed cross-coupling of arylboronic acids with allenoates is documented. The high regio- and stereoselectivity of the process enables a wide range of β-aryl β,γ-unsaturated esters to be prepared in good to excellent yields (up to 95%) and high E / Z -selectivity. Additionally, [3+2]-cascade sequence was observed when 2-formylphenylboronic acid was employed.
Liu, Yang,Daka, Mario,Bandini, Marco
p. 3187 - 3196
(2018/08/17)

Fast Living Polymerization and Helix-Sense-Selective Polymerization of Diazoacetates Using Air-Stable Palladium(II) Catalysts
In this work, air-stable palladium(II) catalysts bearing bidentate phosphine ligands were designed and prepared, which could initiate fast and living polymerizations of various diazoacetate monomers under mild conditions. The polymerization afforded the desired polymers in high yields with controlled molecular weights (Mns) and narrow molecular weight distributions (Mw/Mns). The Mns of the isolated polymers were linearly correlated to the initial feed ratios of monomer to catalyst, confirming the living/controlled manner of the polymerizations. The Mn also increased linearly with the monomer conversion, and all of the isolated polymers showed narrow Mw/Mns. The polymerization was relatively fast and could be accomplished within several minutes. Such fast living polymerization method can be applied to a wide range of diazoacetate monomers in various organic solvents at room temperature in air. Taking advantage of the living nature, we facilely prepared a series of block copolymers through chain extension reactions. The amphiphilic block copolymers synthesized by this method exhibited interesting self-assembly properties. Moreover, polymerization of achiral bulky diazoacetate by Pd(II) catalysts bearing a chiral bidentate phosphine ligand leads to the formation of polymers with high optical activity due to the formation of the predominantly one-handed helix of the main chain. The helix sense of the polymers was determined by the chirality of the Pd(II) catalysts.
Chu, Jia-Hong,Xu, Xun-Hui,Kang, Shu-Ming,Liu, Na,Wu, Zong-Quan
supporting information
p. 17773 - 17781
(2019/01/04)

Phosphine-Catalyzed Domino β/γ-Additions of Benzofuranones with Allenoates: A Method for Unsymmetrical 3,3-Disubstituted Benzofuranones
A phosphine-catalyzed domino process of benzofuranones with allenoates has been developed which furnishes highly functionalized unsymmetrical 3,3-disubstituted benzofuranones in synthetically useful yields. The mechanism for the transformation is a tandem β-umpolung/γ-umpolung process.
Huang, Zhusheng,Yang, Xiuqin,Yang, Fulai,Lu, Tao,Zhou, Qingfa
supporting information
p. 3524 - 3527
(2017/07/17)

BIODEGRADABLE CATIONIC SURFACTANT
PROBLEM TO BE SOLVED: To provide a cationic surfactant with excellent biodegradability while retaining microbicidal properties. SOLUTION: There is provided a compound represented by the general formula (1). [In the formula, L is an oxygen atom or -NH-; R is a hydroxy group, nitro group, C1-6 alkyl group, halogen atom, aldehyde group, or -COOR'; R' is a hydrogen atom or C1-6 alkyl group; n is an integer from 10 to 18; m is an integer from 0 to 5, where, if m is 2 or greater, the multiple R can be identical or different; and X is a halogen atom.] SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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(2018/01/09)

Cycloaddition of Fluorenone N-Aryl Nitrones with Methylenecyclopropanes and Sequential 1,3-Rearrangement: An Entry to Synthesis of Spirofluorenylpiperidin-4-ones
A facile synthesis of various spirofluorenylpiperidin-4-ones has been achieved in good yields from fluorenone N-aryl nitrones and methylenecyclopropanes. This method involved an initial cycloaddition to form a 5-spirocyclopropane-isoxazoline, which underwent a highly selective 1,3-rearrangement to give the desired product. The stereochemistry of the spirofluorenylpiperidin-4-one could be controlled by the cycloaddition and sequential rearrangement strategy. Furthermore, the spirofluorenylpiperidin-4-ones could be not only prepared in one-pot procedure but also converted to useful scaffolds by reduction or oxidation conditions.
Ma, Xiao-Pan,Zhu, Jie-Feng,Wu, Si-Yi,Chen, Chun-Hua,Zou, Ning,Liang, Cui,Su, Gui-Fa,Mo, Dong-Liang
p. 502 - 511
(2017/04/26)

Organocatalyzed Direct Aldol Reaction of Silyl Glyoxylates for the Synthesis of α-Hydroxysilanes
A novel organocatalyzed direct aldol reaction of aldehydes to silyl glyoxylates is disclosed. This method provides an efficient route to α-hydroxysilanes with excellent enantioselectivities (up to 99% ee) and high diastereoselectivities (up to >20:1 dr). In the new activation model of silyl glyoxylates, the hydrogen bond is critical to the reaction. A carbonyl group directly attached to silicon in acylsilanes could be activated by coordination to the proton of hydroxyl and carboxylic acid via a hydrogen bond. Moreover, commercially available cis-l-4-hydroxyproline is an ideal organocatalyst for activating both aldehydes and acylsilanes.
Han, Man-Yi,Xie, Xiaoyu,Zhou, Di,Li, Pinhua,Wang, Lei
supporting information
p. 2282 - 2285
(2017/05/12)

Click synthesis of some mono/bis 1,2,3-triazoles with ester linkage and their microbicidal activity
Synthesis of some new 1,4-disubstituted 1,2,3-triazoles with ester functionality is reported employing Cu(I) catalyzed Huisgen [3+2] cycloaddition reaction of prop-2-yn-1-yl benzoates with 1,4-phenylenebis(methylene) bis(2-azidoacetate) and benzyl 2-azidoacetates. The synthesized compounds were well characterized through FTIR, 1H NMR, 13C NMR and HRMS. Further, the synthesized triazole derivatives were accessed for in vitro antimicrobial activity against one Gram-positive bacterial strain Staphylococcus aureus, three Gram-negative bacterial strains Escherichia coli, Klebsiella pneumoniae, Enterobacter aerogenes and two fungi Candida albicans and Aspergillus niger. Few of the synthesized disubstituted 1,2,3-triazoles displayed moderate to good inhibitory activity against tested microbial strains.
Kaushik,Pahwa, Ashima
p. 2171 - 2176
(2017/10/06)

Regio- and Stereoselective Copper(II)-Catalyzed Hydrosilylation of Activated Allenes in Water: Access to Vinylsilanes
By using catalytic amounts of copper(II), 4-picoline, and dimethylphenylsilylpinacol borane, a series of allenoates were silylated on the β carbon in good to excellent yields and high (E)-selectivity. The mild and efficient silylation method is conducted in water under atmospheric conditions to afford vinylsilanes.
Pashikanti, Srinath,Calderone, Joseph A.,Nguyen, Matthew K.,Sibley, Christopher D.,Santos, Webster L.
supporting information
p. 2443 - 2446
(2016/06/09)

Designing ‘Totem’ C2-Symmetrical Iron Porphyrin Catalysts for Stereoselective Cyclopropanations
The catalytic activity of the iron(III) C2chiral porphyrin Fe(2)(OMe) in alkene cyclopropanation is herein reported. The catalyst promoted the reaction of differently substituted styrenes with diazo derivatives with trans-diastereoselectivities and enantioselectivities up to 99:1 and 87 %, respectively. In addition, high TON and TOF values (up to 10 000 and 120 000 h?1, respectively) were observed indicating good activity and stability of the catalyst in optimized experimental conditions. The study of the cyclopropanation reaction revealed that the porphyrin skeleton is composed of two ‘totem’ parts which were independently responsible for the observed enantio- and diastereoselectivities. To further our research we also investigated the catalytic role of the methoxy axial ligand coordinated to the iron atom. The molecular structure of Fe(2)(OMe) was optimized by DFT calculations which were also employed to achieve a better understanding of the mechanistic details of the carbene transfer reaction.
Carminati, Daniela Maria,Intrieri, Daniela,Caselli, Alessandro,Le Gac, Stéphane,Boitrel, Bernard,Toma, Lucio,Legnani, Laura,Gallo, Emma
supporting information
p. 13599 - 13612
(2016/09/13)

Novel ibuprofen prodrugs with improved pharmacokinetics and non-ulcerogenic potential
In the present study, we evaluated the anti-inflammatory activity with pharmacokinetic, ulcerogenic properties of various synthesized prodrugs of ibuprofen in experimental animals. Prodrugs 2, 6, 9, 10, 12, and 14 were found to possess significant anti-inflammatory activity with almost non-ulcerogenic potential than standard drug ibuprofen 1a in both normal and inflammation-induced rats. Metabolic stability of prodrugs 2, 6, 9, 10, 12, and 14 were also studied in rat liver microsomes and oral bioavailability was determined by estimating area under curve (AUC) and plasma concentration of these prodrugs at various time intervals. The experimental findings elicited higher AUC and plasma concentration at 1 and 2 h indicating improved oral bioavailability as compared to parent ibuprofen. These prodrugs are found to have least gastric ulceration with retain anti-inflammatory activity observed in experimental animals. Therefore, present experimental findings demonstrated significant improvement of various pharmacokinetic properties with least ulcerogenic potential of ester prodrugs of ibuprofen an anti-inflammatory agent
Dhakane, Valmik D.,Chavan, Hemant V.,Thakare, Vishnu N.,Adsul, Laxman K.,Shringare, Sadanand N.,Bandgar, Babasaheb P.
p. 503 - 517
(2014/03/21)

Preparation of a novel silica gel-adsorbed Br?nsted acid catalyst for the solvent-free esterification of bromoacetic acid with benzyl alcohol
A new bifunctional Br?nsted acid catalyst that contains two sulfo groups was prepared. The adsorption of this new bifunctional Br?nsted acid catalyst on silica gel made it possible to be reused 10 times without a loss of catalytic activity in the solvent-free esterification of bromoacetic acid with an equiv. of benzyl alcohol without the formation of dibenzyl ether.
Funabiki, Kazumasa,Komeda, Takuya,Sakaida, Yuta,Kubota, Yasuhiro,Matsui, Masaki
p. 116 - 120
(2013/02/23)

FULLERENE DERIVATIVES
A fullerene derivative having a partial structure represented by formula (1): wherein R represents a monovalent group, and r represents an integer of 0 to 4, in particular, a fullerene derivative, which has one to four structures represented by formula (1), can be applied to an organic photoelectric conversion element having a high open-circuit voltage and is therefore suitable for an organic thin-film solar cell or an organic photosensor, and thus it is extremely useful.
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Page/Page column 9

(2012/06/18)

Human neutrophil elastase phosphonic inhibitors with improved potency of action
Herein, we present the synthesis and the measurement of the inhibitory activity of novel peptidyl derivatives of α-aminoalkylphosphonate diaryl esters as human neutrophil elastase inhibitors. Their selectivity against other serine proteases, including porcine pancreatic elastase, chymotrypsin, and trypsin, was also demonstrated. We also describe the preparation of single peptide diastereomers. The most active and selective compound developed possessed a kinact/KI of 2353000 M-1 s -1, which is the most potent irreversible peptidyl inhibitor of human neutrophil elastase reported to date. The peptidyl inhibitors were demonstrated to be stable in PBS buffer and human plasma, as were their complexes with HNE.
Winiarski, ?ukasz,Oleksyszyn, Józef,Sieńczyk, Marcin
experimental part
p. 6541 - 6553
(2012/09/21)

FULLERENE DERIVATIVE
A fullerene derivative having two or more structures represented by the formula (1) can increase light absorption in a long wavelength range when used for an organic photovoltaic cell. In the formula (1), C1 and C2 represent carbon atoms constituting the fullerene skeleton. m represents an integer from 1 to 6, and n represents an integer from 1 to 4. p represents an integer of 0 or more, and R represents a monovalent organic group. Q represents a single bond, an arylene group, or a divalent heterocyclic group. When m is plurally present, these m may be the same or different from each other.
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Page/Page column 12-13

(2012/09/21)

Convenient synthesis of α-diazoacetates from α-bromoacetates and n,n'-ditosylhydrazine: Preparation of benzyl diazoacetate
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Ideue, Eiji,Toma, Tatsuya,Shimokawa, Jun,Fukuyama, Tohru
p. 501 - 509
(2014/04/17)

FULLERENE DERIVATIVE, COMPOSITION, AND ORGANIC PHOTOELECTRIC CONVERSION ELEMENT
The present invention provides a fullerene derivative represented by the following formula (1). [In formula (1), a ring A represents a fullerene skeleton having 60 or more carbon atoms; R1 and R2 are the same as or different from each other, and each represent a halogen atom, an alkyl group, an alkoxy group or an aryl group (wherein the whole or a part of hydrogen atoms belonging to the alkyl group, the alkoxy group or the aryl group may be substituted with halogen atoms or a halogen atom); m represents an integer of 1 to 6, n represents an integer of 1 to 4, p represents an integer of 0 to 5, w represents an integer of 1 to 6, r represents an integer of 0 to 4, q represents an integer of 0 to 2 and v represents an integer of 0 to 3; when there are a plurality of R1s, the R1s may be the same as or different from each other; when there are a plurality of R2s the R2s may be the same as or different from each other; when there are a plurality of m's, the m's may be the same as or different from each other; and when there are a plurality of q's, the q's may be the same as or different from each other.]
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Page/Page column 11

(2011/08/04)

FULLERENE DERIVATIVE, COMPOSITION AND ORGANIC PHOTOELECTRIC CONVERSION ELEMENT
The present invention provides a fullerene derivative represented by the following formula (1). [In formula (1), a ring A represents a fullerene skeleton having 60 or more carbon atoms; Ar1, Ar2 and Ar3 are the same as or different from each other, and each represent an arylene group; E1, E2, E3 and E4 are the same as or different from each other, and each represent an aryl group; a and b each independently represent 0 or 1, and 0≤a+b1; m represents an integer of 1 to 6, n represents an integer of 1 to 4, p represents an integer of 0 to 5 and r represents an integer of 0 to 4.]
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Page/Page column 11

(2011/08/04)

Design of fulleropyrrolidine derivatives as an acceptor molecule in a thin layer organic solar cell
A systematic study on the design of fulleropyrrolidine derivatives as the acceptor of photovoltaic cells has been carried out using poly(3-hexylthiophene) (P3HT) as the model base polymer. It was found that N-methoxyethoxyethyl-2-(2- methoxyphenyl)fulleropyrrolidine worked as a good acceptor partner with P3HT and a high power conversion efficiency (PCE) (3.44%) was obtained; this is superior to that of the P3HT polymer including methyl [6,6]-phenyl-C61-butylate ([C60]-PCBM) under the same experimental conditions.
Matsumoto, Kei,Hashimoto, Kohji,Kamo, Masaya,Uetani, Yasunori,Hayase, Shuichi,Kawatsura, Motoi,Itoh, Toshiyuki
supporting information; experimental part
p. 9226 - 9230
(2011/05/05)

Cross-dehydrogenative coupling reactions by transition-metal and aminocatalysis for the synthesis of amino acid derivatives
The direct approach: The title coupling reactions of N-aryl glycine esters with unmodified ketones occurred smoothly in the presence of tert-butyl hydroperoxide (TBHP) or 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) under mild conditions (see scheme). The oxidant used for C-H activation determined the selectivity of the reactions for a particular type of ketone substrate. Copyright
Xie, Jin,Huang, Zhi-Zhen
supporting information; experimental part
p. 10181 - 10185
(2011/02/27)

Separation, recovery and reuse of N-heterocyclic carbene catalysts in transesterification reactions
A novel and convenient strategy to separate, recover and reuse N-heterocyclic carbene catalysts in transesterification reactions has been developed.
Zeng, Tieqiang,Song, Gonghua,Li, Chao-Jun
supporting information; experimental part
p. 6249 - 6251
(2010/02/16)

Synthesis of fulleropyrrolidine-imidazolium salt hybrids and their solubility in various organic solvents
Eight types of fulleropyrrolidine-imidazolium hybrids have been synthesized and their solubility determined in various types of organic solvents. The solvent solubility of fullerene derivatives depends on the alky side chain on the imidazolium ring; modification of solvent solubility of the fulleropyrrolidine-imidazolium hybrids has thus been accomplished by introduction of an appropriate alkyl group using imidazoyl moiety as the 'functional group connector'. The imidazolium group seems to act not only as the connector but also as an important functional group that controls the solubility.
Itoh, Toshiyuki,Mishiro, Makoto,Matsumoto, Kei,Hayase, Shuichi,Kawatsura, Motoi,Morimoto, Minoru
p. 1823 - 1828
(2008/09/18)

N,N′-ditosylhydrazine: A convenient reagent for facile synthesis of diazoacetates
A novel entry to the synthesis of diazoacetates is disclosed. A variety of diazoacetates were synthesized from the corresponding bromoacetates by treatment with N,N′-ditosylhydrazine in moderate to high yields. Ease of operation with the stable crystalline reagent as well as a short reaction time offer a useful alternative to the conventional methods.
Torna, Tatsuya,Shimokawa, Jun,Fukuyama, Tohru
p. 3195 - 3197
(2008/02/10)

Proteomimetic compounds and methods
The present invention relates to compounds and pharmaceutical compositions which are proteomimetic and to methods for inhibiting the interaction of an alpha-helical protein with another protein or binding site. Methods for treating diseases or conditions which are modulated through interactions between alpha helical proteins and their binding sites are other aspects of the invention.
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(2008/06/13)

An Expedient Synthesis of Cationic Rhodamine Fluorescent Probes Suitable for Conjugation to Amino Acids and Peptides
Rhodamine 19 benzyloxycarbonylmethyl ester bromide 8 and rhodamine 19 4-chloromethyl-1-phenylmethyl ester chloride 12 act as precursors to cationic fluorescent probes. Molecules containing free amine or carboxylate functional groups, respectively, can be attached in a one-step procedure, yielding the desired probes without the need for chromatographic purification. As a proof of concept the method was applied to the attachment of amino acid and dipeptide residues through either the N- or C-termini. The precursor molecules 8 and 12 are readily synthesized from the inexpensive, commercially available dye rhodamine 6G.
Afonso, Carlos A. M.,Santhakumar,Lough, Alan,Batey, Robert A.
p. 2647 - 2654
(2007/10/03)

Bromoacetyl bromide: A versatile and selective cleaving agent for ethers and acetals
It is shown that bromoacetyl bromide can be utilized for the selective cleavage of ethers and acetals in high yields. With cyclic ethers and acetals as starting materials, cleavage products are produced with two strategically positioned bromo substituents which may be exploited for selective extention of the carbon chain.
Schneider, David F.,Viljoen, Murray S.
p. 721 - 728
(2007/10/03)

Scavenger assisted combinatorial process for preparing libraries of tertiary amine compounds
This invention relates to a novel solution phase process for the preparation of tertiary amine combinatorial libraries. These libraries have utility for drug discovery and are used to form wellplate components of novel assay kits.
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(2008/06/13)

Indole derivatives as 5-HT1-like agonists
Compounds of formula (I) and pharmaceutically acceptable salts thereof, wherein R1 is a substituted alkylene; C3 -C7 cycloalkyl optionally substituted with HO; C3 -C6 alkenyl optionally substituted with aryl; C5 -C7 cycloalkenyl; or C3 -C6 alkynyl; R2 is H; halo; F3 C; NC; R8 R9 NOC; a substituted alkylene; R8 R9 NO2 S; R10 S(O)m ; R12 CON(R11); R10 SO2 N(R11); R8 R9 NOCN(R11); R10 O2 CN(R11); R13 (CH2)n CH=CH; or R7 O are selective 5-HT1 -like receptor agonists useful in the treatment of migraine, cluster headache, chronic paroxysmal hemicrania and headache associated with vascular disorders.
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(2008/06/13)