Mechanisms of Reactions of Sulfinic Acids I
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Norbornene Probes for the Detection of Cysteine Sulfenic Acid in Cells Lisa J
Letters Cite This: ACS Chem. Biol. 2019, 14, 594−598 pubs.acs.org/acschemicalbiology Norbornene Probes for the Detection of Cysteine Sulfenic Acid in Cells Lisa J. Alcock,†,‡ Bruno L. Oliveira,§ Michael J. Deery,∥ Tara L. Pukala,⊥ Michael V. Perkins,† Goncalo̧ J. L. Bernardes,*,§,# and Justin M. Chalker*,†,‡ † Flinders University, College of Science and Engineering, Sturt Road, Bedford Park, South Australia 5042, Australia ‡ Flinders University, Institute for NanoScale Science and Technology, Sturt Road, Bedford Park, South Australia 5042, Australia § Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom ∥ Cambridge Centre for Proteomics, Cambridge Systems Biology Centre, Department of Biochemistry, University of Cambridge, Tennis Court Road, Cambridge CB2 1QW, United Kingdom ⊥ The University of Adelaide, School of Physical Sciences, Adelaide, South Australia 5005, Australia # Instituto de Medicina Molecular, Faculdade de Medicina, Universidade de Lisboa, Avenida Professor Egas Moniz, 1649-028, Lisboa, Portugal *S Supporting Information ABSTRACT: Norbornene derivatives were validated as probes for cysteine sulfenic acid on proteins and in live cells. Trapping sulfenic acids with norbornene probes is highly selective and revealed a different reactivity profile than the traditional dimedone reagent. The norbornene probe also revealed a superior chemoselectivity when compared to a commonly used dimedone probe. Together, these results advance the study of cysteine oxidation in biological systems. -
Pyramidalization/Twisting of the Amide Functional Group Via Remote Steric Congestion Triggered by Metal Coordination Chemical Science
Chemical Volume 8 Number 1 January 2017 Pages 1–810 Science rsc.li/chemical-science ISSN 2041-6539 EDGE ARTICLE Naoya Kumagai, Masakatsu Shibasaki et al. Pyramidalization/twisting of the amide functional group via remote steric congestion triggered by metal coordination Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue Pyramidalization/twisting of the amide functional group via remote steric congestion triggered by Cite this: Chem. Sci.,2017,8,85 metal coordination† Shinya Adachi, Naoya Kumagai* and Masakatsu Shibasaki* For decades, the planarity of the amide functional group has garnered sustained interest in organic chemistry, enticing chemists to deform its usually characteristic high-fidelity plane. As opposed to the construction of amides that are distorted by imposing rigid covalent bond assemblies, we demonstrate herein the deformation of the amide plane through increased steric bulk in the periphery of the amide moiety, which is induced by coordination to metal cations. A crystallographic analysis revealed that the thus obtained amides exhibit significant pyramidalization and twisting upon coordination to the metals, Received 16th August 2016 while the amide functional group remained intact. The observed deformation, which should be Accepted 21st September 2016 attributed to through-space interactions, substantially enhanced the solvolytic cleavage of the amide, DOI: 10.1039/c6sc03669d Creative Commons Attribution 3.0 Unported Licence. providing compelling evidence that temporary crowding in the periphery -
Empowering Alcohols As Carbonyl Surrogates for Grignard-Type Reactions
ARTICLE https://doi.org/10.1038/s41467-020-19857-9 OPEN Empowering alcohols as carbonyl surrogates for Grignard-type reactions Chen-Chen Li 1, Haining Wang1, Malcolm M. Sim1, Zihang Qiu 1, Zhang-Pei Chen1, Rustam Z. Khaliullin1 & ✉ Chao-Jun Li 1 The Grignard reaction is a fundamental tool for constructing C-C bonds. Although it is widely used in synthetic chemistry, it is normally applied in early stage functionalizations owing to 1234567890():,; poor functional group tolerance and less availability of carbonyls at late stages of molecular modifications. Herein, we report a Grignard-type reaction with alcohols as carbonyl surro- gates by using a ruthenium(II) PNP-pincer complex as catalyst. This transformation proceeds via a carbonyl intermediate generated in situ from the dehydrogenation of alcohols, which is followed by a Grignard-type reaction with a hydrazone carbanion to form a C-C bond. The reaction conditions are mild and can tolerate a broad range of substrates. Moreover, no oxidant is involved during the entire transformation, with only H2 and N2 being generated as byproducts. This reaction opens up a new avenue for Grignard-type reactions by enabling the use of naturally abundant alcohols as starting materials without the need for pre-synthesizing carbonyls. 1 Department of Chemistry and FQRNT Centre for Green Chemistry and Catalysis, McGill University, 801 Sherbrooke Street West, Montreal, QC H3A 0B8, ✉ Canada. email: [email protected] NATURE COMMUNICATIONS | (2020) 11:6022 | https://doi.org/10.1038/s41467-020-19857-9 | www.nature.com/naturecommunications 1 ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-020-19857-9 n tandem with the significant advancements of biological and even be successfully applied in synergistic relay reactions29. -
Synthesis of Optically Pure Macroheterocycles with 2,6-Pyridinedicarboxylic and Adipic Acid Fragments from ∆3-Carene
Macrolides Paper Макролиды Статья DOI: 10.6060/mhc190660y Synthesis of Optically Pure Macroheterocycles with 2,6-Pyridinedicarboxylic and Adipic Acid Fragments from ∆3-Carene Marina P. Yakovleva,@ Kseniya S. Denisova, Galina R. Mingaleeva, Valentina A. Vydrina, and Gumer Yu. Ishmuratov Ufa Institute of Chemistry, Ufa Federal Research Center, Russian Academy of Sciences, 450054 Ufa, Russia @Corresponding author E-mail: [email protected] Based on the available natural monoterpene ∆3-carene we have developed the synthesis of four optically pure macroheterocycles with ester and dihydrazide fragments through the intermediate 1-((1S,3R)-3-(2-hydroxyethyl- 2,2-dimethylcyclopropyl)propan-2-one using its [2+1]-interaction with dichloranhydrides of adipic or 2,6-pyridinedicarboxylic acids and [1+1]-condensation of the obtained α,ω-diketodiesters with dihydrazides of adipic or 2,6-pyridinedicarboxylic acids. The structure of new compounds was confirmed by IR and NMR spectroscopy and mass spectrometry. Keywords: 3-Carenes, ozonolysis, sodium hypochlorite, macroheterocycles with ester and dihydrazide fragments, [2+1] and [1+1] condensations, synthesis. Синтез оптически чистых макрогетероциклов со сложноэфирными и дигидразидными фрагментами адипиновой и 2,6-пиридиндикарбоновой кислот из D3-карена М. П. Яковлева,@ К. С. Денисова, Г. Р. Мингалеева, В. А. Выдрина, Г. Ю. Ишмуратов Уфимский Институт химии – обособленное структурное подразделение Федерального бюджетного научного учреждения Уфимского федерального исследовательского центра Российской академии -
Six New Induced Sesquiterpenes from the Cultures of Ascomycete Daldinia Concentrica Xiang-Dong Qin, Hong-Jun Shao, Ze-Jun Dong, Ji-Kai Liu
J. Antibiot. 61(9): 556–562, 2008 THE JOURNAL OF ORIGINAL ARTICLE ANTIBIOTICS Six New Induced Sesquiterpenes from the Cultures of Ascomycete Daldinia concentrica Xiang-Dong Qin, Hong-Jun Shao, Ze-Jun Dong, Ji-Kai Liu Received: April 23, 2008 / Accepted: August 19, 2008 © Japan Antibiotics Research Association Abstract Six new sesquiterpenes having the botryane production titers of desired compounds. This approach was carbon skeleton (1ϳ6), together with known compounds successfully used as a valuable tool to exploit natural (7ϳ10) were induced and isolated from the ascomycete products diversity in the past, for example, actinomycetes Daldinia concentrica (strain S 0318). Structures (Streptomyces sp.) and fungi (Aspergillus sp., elucidation was accomplished by NMR spectroscopic and Sphaeropsidales sp.) produce additional compounds after X-ray crystallographic studies. variation of the culture conditions [3ϳ5]. Previous investigation reported the isolation of induced Keywords Sesquiterpenes, Daldinia concentrica, daldinins A, B, and C with a new skeleton and four known ascomycete, induction, botryane compounds from the cultures of ascomycete Daldinia concentrica [6]. Following the OSMAC approach, the strain S 0318 (Daldinia concentrica) has been cultivated Introduction and further investigated. In the culture broth extract from Erlenmeyer flasks (color, transparent; size, 500 ml; media, Fungi or bacteria that produce secondary metabolites often 300 ml) instead of reagent bottles under same cultivation have the potential to produce various compounds from a conditions we detected additional metabolites by TLC and single strain. Variation of cultivation parameters to induce HPLC. Careful investigation on the culture of D. the production of formerly unknown compounds is one of concentrica strain (S 0318) led to the isolation of new the approach to increase the number of secondary compounds methyl-7a-acetoxydeacetylbotryoloate (1), 7a- metabolites from one single organism. -
Studies on the Chemistry of Paclitaxel
STUDIES ON THE CHEMISTRY OF PACLITAXEL Haiqing Yuan Dissertation submitted to the Faculty of the Virginia Polytechnic Institute and State University in the partial fulfillment of the requirement for the degree of Doctor of Philosophy in Chemistry Dr. David G. I. Kingston, Chair Dr. Michael Calter Dr. Neal Castagnoli, Jr. Dr. Richard Gandour Dr. Larry Taylor August 11, 1998 Blacksburg, Virginia Keywords: Paclitaxel, Taxol®, synthesis, analog, SAR Copyright 1998, Haiqing Yuan STUDIES ON THE CHEMISTRY OF PACLITAXEL HAIQING YUAN (ABSTRACT) Paclitaxel is a natural occurring diterpene alkaloid originally isolated from the bark of Taxus brevifolia. It is now one of the most important chemotherapeutic agents for clinical treatment of ovarian and breast cancers. Recent clinical trials have also shown paclitaxel’s potential for the treatment of non-small-cell lung cancer, head and neck cancer, and other types of cancers. While tremendous chemical research efforts have been made in the past years, which established the fundamental structure-activity relationships of the paclitaxel molecule, and provided analogs for biochemical studies to elucidate the precise mechanism of action and for the development of second-generation agents, many areas remain to be explored. In continuation of our efforts in the structure-activity relationships study of A- norpaclitaxel, five new analogs modified at the C-1 substituent and analogs with expanded B-ring or contracted C-ring have now been prepared. Preliminary biological studies indicated that the volume rather than functionality at the C-1 position plays a role in determining the anticancer activity by controlling the relative position of the tetracyclic ring system, which in turn controls the positions of the most critical functionalities such as the C-2 benzoyl, the C-4 acetate, and the C-13 side chain. -
Microwave Assisted Synthesis, Spectral and Antimicrobial Evaluation of Hydrazones and Their Metal Complexes
Devendra Kumar et al. / Journal of Pharmacy Research 2012,5(2),830-834 Research Article Available online through ISSN: 0974-6943 http://jprsolutions.info Microwave assisted synthesis, spectral and antimicrobial evaluation of hydrazones and their metal complexes Devendra Kumar ,Shivani Singh,Neelam,Rubeena Akhtar Department of Chemistry, Institute of Basic Sciences,Dr. B. R. Ambedkar University, Khandari Campus, Agra-282002 Received on:19-12-2011; Revised on: 07-01-2012; Accepted on:28-01-2012 ABSTRACT Six new metal complexes of Co (II), Ni (II) and Cu (II) with bis-(furfuryl) adipic acid dihydrazone (FADH) and bis- (2-acetyl thiophene) adipic acid dihydrazone (2-ATADH) have been synthesized under microwave irradiation. The Microwave irradiation method was found remarkably successful and gave higher yield at less reaction time. All the synthesized compounds have been characterized by running their TLC for single spot, repeated melting point determinations, elemental analyses, IR, 1H-NMR and electronic spectral studies. The elemental analyses and spectral analysis results revealed their Metal: Ligand (1:1) stoichiometry. All the synthesized compounds have been screened in vitro for their antibacterial activity against Staphylococcus aureus, Pseudomonas aeruginosa and also for their antifungal activity against Aspergillus niger and Candida albicans. Key words: Synthesis, Microwave irradiation, Spectral, Antibacterial, Antifungal. INTRODUCTION Over the last few years, there has been growing interest in the synthesis of Synthesis of diethyl adipate: 14.6 g (0.1M) adipic acid was dissolved in organic compounds under green or sustainable chemistry such as micro- 20 ml absolute alcohol. To this solution, 3ml conc. H2SO4 was added. The wave irradiation because of increasing environmental consciousness. -
Synthesis of Macrocyclic Bis-Hydrazone and Their Use in Metal Cations Extraction
International Scholarly Research Network ISRN Organic Chemistry Volume 2012, Article ID 208284, 8 pages doi:10.5402/2012/208284 Research Article Synthesis of Macrocyclic Bis-Hydrazone and Their Use in Metal Cations Extraction Farouk Kandil, Mohamad Khaled Chebani, and Wail Al Zoubi Department of Chemistry, Faculty of Science, University of Damascus, Damascus, Syria Correspondence should be addressed to Wail Al Zoubi, [email protected] Received 9 October 2011; Accepted 30 October 2011 Academic Editor: G. Li Copyright © 2012 Farouk Kandil et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Two new macrocyclic hydrazone Schiff bases were synthesized by reaction of succindihydrazide and adipdihydrazide with acetylacetone. Hydrazones have been characterized by elemental analyses and IR, mass, 1HNMR,and 13C NMR spectral data. Hydrazones have been studied by liquid-liquid extraction towards the s-metal ions (Li+,Na+,andK+)andd-metalions(Cu2+ and Cr3+) from aqueous phase to organic phase. The effect of chloroform and dichloromethane as organic solvents over the metal chlorides extraction was investigated at 25 ± 0.1◦C by using flame atomic absorption. We found differences between the two solvents in extraction selectivity. 1. Introduction Five dissymmetric tridentate Schiff base ligands contain- ing a mixed donor set of ONN and ONO were prepared by ff Hydrazones are special class of compounds in the Schi bases the reaction of benzohydrazide with the appropriate salicy- family. They are characterized by the presence of the follow- laldehyde and pyridine-2-carbaldehyde and characterized by ing FT-IR, 1HNMR,and13CNMR[13]. -
Acetoxy Drug: Protein Transacetylase: a Novel Enzyme-Mediating Protein Acetylation by Polyphenolic Peracetates*
Pure Appl. Chem., Vol. 77, No. 1, pp. 245–250, 2005. DOI: 10.1351/pac200577010245 © 2005 IUPAC Acetoxy drug: protein transacetylase: A novel enzyme-mediating protein acetylation by polyphenolic peracetates* Hanumantharao G. Raj1,‡, Brajendra K. Singh2, Ekta Kohli1, B. S. Dwarkanath3, Subhash C. Jain2, Ramesh C. Rastogi2, Ajit Kumar1, J. S. Adhikari3, Arthur C. Watterson4, Carl E. Olsen5, and Virinder S. Parmar2 1Biochemistry Department, V. P. Chest Institute, University of Delhi, Delhi 110 007, India; 2Bioorganic Laboratory, Department of Chemistry, University of Delhi, Delhi 110 007, India; 3Institute of Nuclear Medicine and Allied Sciences, Lucknow Road, Delhi 110 054, India; 4INSET, Department of Chemistry, University of Massachusetts, Lowell, MA 01854, USA; 5Department of Chemistry, Royal Veterinary and Agricultural University, DK-1871 Frederiksburg C, Copenhagen, Denmark Abstract: The acetylation of proteins in biological systems is largely catalyzed by specific acetyl transferases utilizing acetyl CoA as the acetyl donor. The enzymatic acetylation of pro- teins independent of acetyl CoA was unknown until we discovered a unique membrane- bound enzyme in mammalian cells catalyzing the transfer of acetyl groups from polypheno- lic peracetates (PAs) to certain enzyme proteins, resulting in the modulation of their catalytic activities. Since for the enzyme, acetyl derivatives of several classes of polyphenols such as coumarins, flavones, chromones, and xanthones were found to be acetyl donors, the enzyme was termed as acetoxy drug: protein transacetylase (TAase). TAase was found to be ubiqui- tously present in tissues of several animal species and a variety of animal cells. Liver micro- somal cytochrome P-450 (CYP), NADPH-cytochrome c reductase and cytosolic glutathione S-transferase (GST) were found to be the targets for TAase-catalyzed acetylation by the model acetoxy drug 7,8-diacetoxy-4-methylcoumarin (DAMC). -
Technical Notes
1624 Bioconjugate Chem. 2005, 16, 1624−1628 TECHNICAL NOTES Synthesis of Chemical Probes to Map Sulfenic Acid Modifications on Proteins Leslie B. Poole,†* Bu-Bing Zeng,‡,| Sarah A. Knaggs,‡ Mamudu Yakubu,§ and S. Bruce King‡,* Departments of Chemistry and Biochemistry, Wake Forest University, Winston-Salem, North Carolina 27109, and Department of Chemistry, Elizabeth City State University, Elizabeth City, North Carolina 27909 . Received August 23, 2005 Cysteine sulfenic acids in proteins can be identified by their ability to form adducts with dimedone, but this reagent imparts no spectral or affinity tag for subsequent analyses of such tagged proteins. Given its similar reactivity toward cysteine sulfenic acids, 1,3-cyclohexadione was synthetically modified to an alcohol derivative and linked to fluorophores based on isatoic acid and 7-methoxycou- marin. The resulting compounds retain full reactivity and specificity toward cysteine sulfenic acids in proteins, allowing for incorporation of the fluorescent label into the protein and “tagging” it based on its sulfenic acid redox state. Control experiments using dimedone further show the specificity of the reaction of 1,3-diones with protein sulfenic acids in aqueous media. These new compounds provide the basis for an improved method for the detection of protein sulfenic acids. INTRODUCTION Scheme 1 Interest in the identification of cysteine sulfenic acids in proteins by biochemists has grown substantially over the past decade as their biological roles in redox regula- tion and catalysis within an array of cellular proteins have become better defined (1, 2). Despite their impor- tance, only a limited set of tools to identify these species exist, and most of these are only applicable to in vitro studies of pure, isolated proteins (3, 4). -
THIOL OXIDATION a Slippery Slope the Oxidation of Thiols — Molecules RSH Oxidation May Proceed Too Predominates
RESEARCH HIGHLIGHTS Nature Reviews Chemistry | Published online 25 Jan 2017; doi:10.1038/s41570-016-0013 THIOL OXIDATION A slippery slope The oxidation of thiols — molecules RSH oxidation may proceed too predominates. Here, the maximum of the form RSH — can afford quickly for intermediates like RSOH rate constants indicate the order − − − These are many products. From least to most to be spotted and may also afford of reactivity: RSO > RS >> RSO2 . common oxidized, these include disulfides intractable mixtures. Addressing When the reactions are carried out (RSSR), as well as sulfenic (RSOH), the first problem, Chauvin and Pratt in methanol-d , the obtained kinetic reactions, 1 sulfinic (RSO2H) and sulfonic slowed the reactions down by using isotope effect values (kH/kD) are all but have (RSO3H) acids. Such chemistry “very sterically bulky thiols, whose in the range 1.1–1.2, indicating that historically is pervasive in nature, in which corresponding sulfenic acids were no acidic proton is transferred in the been very disulfide bonds between cysteine known to be isolable but were yet rate-determining step. Rather, the residues stabilize protein structures, to be thoroughly explored in terms oxidations involve a specific base- difficult to and where thiols and thiolates often of reactivity”. The second problem catalysed mechanism wherein an study undergo oxidation by H2O2 or O2 in was tackled by modifying the model acid–base equilibrium precedes the order to protect important biological system, 9-mercaptotriptycene, by rate-determining nucleophilic attack − − − structures from damage. Among including a fluorine substituent to of RS , RSO or RSO2 on H2O2. the oxidation products, sulfenic serve as a spectroscopic handle. -
Cysteine Sulfenic Acid As an Intermediate in Disulfide Bond Formation and Nonenzymatic Protein Folding† Douglas S
7748 Biochemistry 2010, 49, 7748–7755 DOI: 10.1021/bi1008694 Cysteine sulfenic Acid as an Intermediate in Disulfide Bond Formation and Nonenzymatic Protein Folding† Douglas S. Rehder and Chad R. Borges* Molecular Biomarkers, The Biodesign Institute at Arizona State University, Tempe, Arizona 85287 Received May 28, 2010; Revised Manuscript Received July 22, 2010 ABSTRACT: As a posttranslational protein modification, cysteine sulfenic acid (Cys-SOH) is well established as an oxidative stress-induced mediator of enzyme function and redox signaling. Data presented herein show that protein Cys-SOH forms spontaneously in air-exposed aqueous solutions of unfolded (disulfide-reduced) protein in the absence of added oxidizing reagents, mediating the oxidative disulfide bond formation process key to in vitro, nonenzymatic protein folding. Molecular oxygen (O2) and trace metals [e.g., copper(II)] are shown to be important reagents in the oxidative refolding process. Cys-SOH is also shown to play a role in spontaneous disulfide-based dimerization of peptide molecules containing free cysteine residues. In total, the data presented expose a chemically ubiquitous role for Cys-SOH in solutions of free cysteine-containing protein exposed to air. In the early 1960s, Anfinsen and colleagues conducted seminal ous oxidants such as hydrogen peroxide are required to build up studies in protein disulfide bond formation and folding, showing significant quantities of Cys-SOH within fully folded proteins. that unfolded (disulfide-reduced) proteins will spontaneously In general, Cys-SOH is a transient intermediate that until the and completely refold, regenerating full protein activity, over a past decade has been difficult to study. It has been understood period of approximately a day in the absence of denaturants that Cys-SOH likely renders the sulfur atom of cysteine electro- (1-6).