Boronic Acid Reagents

Total Page:16

File Type:pdf, Size:1020Kb

Boronic Acid Reagents T10E-H10E Boronic acid reagents Boronic acids are alkyl or aryl substituted carbon to a boron di-iol group (class of organoboranes): . R-B(OH)2 . As Lewis acids, this chemical functional group is capable of forming reversible covalent complexes with sugars, amino acids, hydroxamic acids, etc. The pKa of a boronic acid is ~9, but upon complexion in aqueous solutions, they form tetrahedral boronate complexes with pKa ~7. Hence, boronic acids drive unique features and applications: Boronic acids chemical building blocks are also used in organic chemistry (i.e. Suzuki coupling: R-B(OH)2 + R’-X ► R-R’ ; transmetallation of its organic residue to a transition metal). =>ask at [email protected] See exemples in article and in catalog [cat.Fine.201606] . Boronic acid conjugates of fluorescent dyes are used in biosciences to bind to saccharides for fluorescent detection, for selective transport of saccharides across membranes, or to block certain proteasomes. =>see Fluorescent boronic conjugates: Boronic derivate with Dansyl #FP-M1201A and Eosin #FP-CJ0760 Coumarin Boronic Acid (Cba) Onoo Fluorescent Probe (332/400NM), #FP-1D1401, 10-50-100mg Boronic acid conjugated supports are used for affinity =>see Boronic functionalized supports for affinity purification. See PH-BB190b Boronic acid on magnetic beads, 1µm, 2.5% (w/v) #7A2610, 2ml Related products lines Interbiotec - BioSciences innovation – proposes a complete range of products for protein biochemistry. Products HighLights Overview, including: Remarkable conjugation tools: PEO crosslinkers (hydrophilic spacers), Hydrazone chemistry (flexible method using stable activation step), Click Chemistry & Staudinger ligation (versatile and mild conjugation), Multifunctional cross-linkers, Boronic acid (modifying saccharides) Photoreactive Amino Acids & UV Lamps for crosslinking Label Transfer Reagents Other crosslinkers (i.e. Sulfo-SANPAH, BS3, ...) FluoProbes labeling agents (superior fluorescent dyes) Desalting tools – CelluSep tubings, SpectraPor tubings, GebaFlex, FloatALyser, SlideALyser,... Information inquire Reply by Fax : +33 (0) 4 70 03 82 60 or email at [email protected] □ I wish to receive the complete documentation about: _______________________________________________________ _________________________________________________________________________________________________________________ Name: _____________________ 2nd name:__________________ Position:____________________ Company/Institute: ___________________________ Service, Lab:_____________________________ Adress: _________________________________________________________________ Zip code: _________ Town: ___________________ Tel____________________ Fax___________________ Email: ____________________________________ .
Recommended publications
  • Design and Synthesis of FRET-Based Boronic Acid Receptors to Detect Carbohydrate Clustering and Development of Diacylglycerol-Ba
    University of Tennessee, Knoxville Trace: Tennessee Research and Creative Exchange Masters Theses Graduate School 12-2009 Design and Synthesis of FRET-Based Boronic Acid Receptors to Detect Carbohydrate Clustering and Development of Diacylglycerol-Based Lipid Probesto Investigate Lipid-Protein Binding Interactions Manpreet Kaur Cheema University of Tennessee - Knoxville Recommended Citation Cheema, Manpreet Kaur, "Design and Synthesis of FRET-Based Boronic Acid Receptors to Detect Carbohydrate Clustering and Development of Diacylglycerol-Based Lipid Probesto Investigate Lipid-Protein Binding Interactions. " Master's Thesis, University of Tennessee, 2009. https://trace.tennessee.edu/utk_gradthes/517 This Thesis is brought to you for free and open access by the Graduate School at Trace: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Masters Theses by an authorized administrator of Trace: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a thesis written by Manpreet Kaur Cheema entitled "Design and Synthesis of FRET-Based Boronic Acid Receptors to Detect Carbohydrate Clustering and Development of Diacylglycerol-Based Lipid Probesto Investigate Lipid-Protein Binding Interactions." I have examined the final electronic copy of this thesis for form and content and recommend that it be accepted in partial fulfillment of the requirements for the degree of Master of Science, with a major in Chemistry. Michael Best, Major
    [Show full text]
  • 1 Structure, Properties, and Preparation of Boronic Acid Derivatives Overview of Their Reactions and Applications Dennis G
    j1 1 Structure, Properties, and Preparation of Boronic Acid Derivatives Overview of Their Reactions and Applications Dennis G. Hall 1.1 Introduction and Historical Background Structurally, boronic acids are trivalent boron-containing organic compounds that possess one carbon-based substituent (i.e., a CÀB bond) and two hydroxyl groups to fill the remaining valences on the boron atom (Figure 1.1). With only six valence electrons and a consequent deficiency of two electrons, the sp2-hybridized boron atom possesses a vacant p-orbital. This low-energy orbital is orthogonal to the three substituents, which are oriented in a trigonal planar geometry. Unlike carbox- ylic acids, their carbon analogues, boronic acids, are not found in nature. These abiotic compounds are derived synthetically from primary sources of boron such as boric acid, which is made by the acidification of borax with carbon dioxide. Borate esters, one of the key precursors of boronic acid derivatives, are made by simple dehydration of boric acid with alcohols. The first preparation and isolation of a boronic acid was reported by Frankland in 1860 [1]. By treating diethylzinc with triethylborate, the highly air-sensitive triethylborane was obtained, and its slow oxidation in ambient air eventually provided ethylboronic acid. Boronic acids are the products of a twofold oxidation of boranes. Their stability to atmospheric oxidation is considerably superior to that of borinic acids, which result from the first oxidation of boranes. The product of a third oxidation of boranes, boric acid, is a very stable and relatively benign compound to humans (Section 1.2.2.3). Their unique properties and reactivity as mild organic Lewis acids, coupled with their stability and ease of handling, are what make boronic acids a particularly attractive class of synthetic intermediates.
    [Show full text]
  • Synthesis and Improvement of Self-Healing Boronate Ester Hydrogels
    SYNTHESIS AND IMPROVEMENT OF SELF-HEALING BORONATE ESTER HYDROGELS By CHRISTOPHER CHI-LONG DENG A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 2017 © 2017 Christopher Chi-long Deng To friends and family and loved ones departed ACKNOWLEDGMENTS Numerous people have supported me to this point. I would like to thank all of my previous teachers throughout my education for the foundation they gave to me and the valuable work that they do for all students. I thank Dr. Yi Zhang for allowing me to work in her lab and gain valuable experience. I would also like to thank Dr. Bill Dolbier for sharing his passion for organic chemistry and assisting me in entering graduate school. Of course, I am grateful towards Dr. Brent Sumerlin for accepting me in his group. His expectations and guidance have been valuable in my scientific growth. Also, I would like to thank my committee of Dr. Ken Wagener, Dr. Stephen Miller, Dr. Adam Veige, and Dr. Anthony Brennan. I appreciate the time taken from their busy schedules and their advice over the years. I would also like to acknowledge the University of Florida, the Department of Chemistry, and the Butler Polymer Laboratory for the opportunity to pursue my doctorate and providing a supportive environment for myself and all graduate students. I am grateful to the members of the Sumerlin group. I have the most interaction with them on a daily basis, and it has been a tremendous source of support both personally and professionally.
    [Show full text]
  • Chemistry Research Report
    Contents 3 Welcome 5 Profiles 37 Publications 51 Staff and students 55 Student prizes & scholarships 58 Ruth Gall profile 60 Graduates of 2017 Front cover: Portrait of A/Prof. Ruth Gall (1923-2017), the first woman to Head the School of Chemistry at the University of Sydney, painted by local artist Dr Kate Gradwell. The School of Chemistry at the University of Sydney is one of the main centres for chemical research and education in Australia and has access to a comprehensive range of modern research and teaching facilities. The School attracts an outstanding cohort of undergraduate students including talented students from all states of Australia. It has a large cohort of both local and international postgraduate research students and offers a vibrant and world class research environment. GENERAL INFORMATION 3 WELCOME HEAD OF SCHOOL Professor Phil Gale at such conferences, reflecting both the excellence of the Head of School School of Chemistry research they are undertaking and their outstanding ability to present this to an audience. Highlights of the awards to staff and students in 2017 include the RJW Le Fèvre Memorial Prize to A/Prof Deanna D’Alessandro; Dr Ivan Kassal was the recipient of the Tall Poppy Award; A/Prof Liz New was a finalist in the 3M Eureka Prize for emerging leader in science; Prof Kate Jolliffe was awarded A.J. Birch Medal; Mr Phil Karpati was the global winner of the 2017 Undergraduate Awards - Phil was also awarded a 2017 Westpac Future Leaders scholarship; and the RACI Cornforth Medal for the best PhD thesis in Australia went to Ms Amandeep Kaur.
    [Show full text]
  • Applications of Boronic Acids in Organic Synthesis
    Applications of Boronic Acids in Organic Synthesis A dissertation presented by Pavel Starkov in partial fulfilment of the requirements for the award of the degree of DOCTOR OF PHILOSOPHY at UNIVERSITY COLLEGE LONDON Department of Chemistry Christopher Ingold Laboratories University College London 20 Gordon Street WC1H 0AJ London Declaration This dissertation is the result of my own work. Where information has been derived from other sources it has been clearly indicated so and acknowledged accordingly. /Pavel Starkov/ ii Abstract This thesis describes progress on the application of boronic acids and borate esters as catalysts and reagents in synthetic organic synthesis, focusing on two areas: one-pot enolate formation/aldol reactions and amide bond formation. Chapter 1 introduces the reader to boronic acids and derivatives thereof, their methods of preparation and their use in synthetic organic chemistry as reactants, reagents and catalysts. Chapter 2 covers current chemical methods and cellular alternatives for amide bond formation. Here, we also discuss our use of boron reagents for the activation of carboxylic acids as well as amides. Chapter 3 introduces a new concept in catalytic aldol reactions, i.e. an alternative strategy to access boron enolates in situ. The work covers successful demonstration of the feasibility of such an approach on an intramolecular system. A novel variation of aerobic Chan–Evans– Lam coupling, an intramolecular coupling of an aliphatic alcohol with a boronic acid using catalytic copper, is also introduced Chapter 4 builds on our observations on gold catalysis and especially that in relation to electrophilic halogenations. Chapter 5 contains full details of the experimental procedures.
    [Show full text]
  • Boronic Acids
    Boronic Acids Boronic Acids www.alfa.com INCLUDING: • Boronic Esters • Oxazaborolidine Reagents • Coupling and Hydroboration Catalysts • Phosphine Ligands • Borylation Reagents www.alfa.com Where Science Meets Service Quality Boronic Acids from Alfa Aesar Alfa Aesar is known worldwide for a variety of chemical compounds used in research and development. Recognized for purity and quality, our products and brands are backed by technical and sales teams dedicated to providing you the best service possible. In this catalog, you will find details on our line of boronic acids, esters and related compounds, which are manufactured to the same exacting standards as our full offering of over 33,000 products. Also included in this catalog is a 28-page introduction to boronic acids, their properties and applications. This catalog contains only a selection of our wide range of chemicals and materials. Also included is a selection of novel coupling catalysts and ligands. Many more products, including high purity metals, analytical products, and labware are available in our main catalog or online at www.alfa.com. Table of Contents About Us _____________________________________________________________________________ II How to Order/General Information ____________________________________________________ III Introduction __________________________________________________________________________ 1 Alkenylboronic acids and esters _____________________________________________________ 29 Alkylboronic acids and esters ________________________________________________________
    [Show full text]
  • Boronic Acids As Prospective Inhibitors of Metallo–Lactamases: Efficient Chemical Reaction in the Enzymatic Active Site Reveal
    molecules Article Boronic Acids as Prospective Inhibitors of Metallo-β-Lactamases: Efficient Chemical Reaction in the Enzymatic Active Site Revealed by Molecular Modeling Alexandra V. Krivitskaya 1 and Maria G. Khrenova 1,2,* 1 Bach Institute of Biochemistry, Federal Research Centre “Fundamentals of Biotechnology” of the Russian Academy of Sciences, 119071 Moscow, Russia; [email protected] 2 Department of Chemistry, Lomonosov Moscow State University, 119991 Moscow, Russia * Correspondence: [email protected] Abstract: Boronic acids are prospective compounds in inhibition of metallo-β-lactamases as they form covalent adducts with the catalytic hydroxide anion in the enzymatic active site upon binding. We compare this chemical reaction in the active site of the New Delhi metallo-β-lactamase (NDM-1) with the hydrolysis of the antibacterial drug imipenem. The nucleophilic attack occurs with the energy barrier of 14 kcal/mol for imipenem and simultaneously upon binding a boronic acid inhibitor. A boron atom of an inhibitor exhibits stronger electrophilic properties than the carbonyl carbon atom of imipenem in a solution that is quantified by atomic Fukui indices. Upon forming the prereaction complex between NDM-1 and inhibitor, the lone electron pair of the nucleophile interacts with the vacant p-orbital of boron that facilitates the chemical reaction. We analyze a set of boronic acid compounds with the benzo[b]thiophene core complexed with the NDM-1 and propose quantitative Citation: Krivitskaya, A.V.; structure-sroperty relationship (QSPR) equations that can predict IC50 values from the calculated Khrenova, M.G. Boronic Acids as descriptors of electron density. These relations are applied to classify other boronic acids with the Prospective Inhibitors of same core found in the database of chemical compounds, PubChem, and proposed ourselves.
    [Show full text]
  • Structure and Properties of 1,3-Phenylenediboronic Acid: Combined Experimental and Theoretical Investigations
    crystals Article Structure and Properties of 1,3-Phenylenediboronic Acid: Combined Experimental and Theoretical Investigations Agnieszka Adamczyk-Wo´zniak 1,*, Michał K. Cyra ´nski 2, Krzysztof Durka 1 , Jan T. Gozdalik 1, Paulina Klimentowska 2, Rafał Rusiecki 1,3, Andrzej Sporzy ´nski 1 and Dorota Zarzecza ´nska 4 1 Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland; [email protected] (K.D.); [email protected] (J.T.G.); [email protected] (R.R.); [email protected] (A.S.) 2 Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland; [email protected] (M.K.S.); [email protected] (P.K.) 3 Adamed Pharma S.A., Pie´nków, Adamkiewicza 6A, 05-152 Czosnów, Poland 4 Faculty of Chemistry, University of Gda´nsk,Wita Stwosza 63, 80-308 Gda´nsk,Poland; [email protected] * Correspondence: [email protected]; Tel.: +48-22-234-6147; Fax: +48-22-628-2741 Received: 16 January 2019; Accepted: 15 February 2019; Published: 19 February 2019 Abstract: The structure and properties of 1,3-phenylenediboronic acid are reported. Molecular and crystal structures were determined by single crystal as well as by powder X-ray diffraction methods. Acidity constant, thermal behavior, and NMR characterization of the title compound were also investigated. In addition to the experimental data, calculations of rotational barrier and intermolecular interaction energies were performed. The compound reveals a two-step acid–base equilibrium with different pKa values. TGA and DSC measurements show a typical dehydration reaction with formation of boroxine.
    [Show full text]
  • Saccharide Recognition : Boronic Acids As Receptors in Polymeric Networks
    IBMT Saccharide Recognition – Boronic Acids as Receptors in Polymeric Networks Dissertation zur Erlangung des akademischen Grades „doctor rerum naturalium “ (Dr. rer. nat.) in der Wissenschaftsdisziplin Physikalische Chemie eingereicht an der Mathematisch-Naturwissenschaftlichen Fakultät der Universität Potsdam von Soeren Schumacher Potsdam, Februar 2011 Published online at the Institutional Repository of the University of Potsdam: URL http://opus.kobv.de/ubp/volltexte/2011/5286/ URN urn:nbn:de:kobv:517-opus-52869 http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-52869 To my parents Acknowledgement During more than three years of research many inspiring discussions, fruitful collaborations and important friendships developed. Since “science” is a discipline in which team- work is essential, this is the place to express my gratitude to many people. They all contributed to this thesis in many different ways and just their support enabled me to write this thesis. I would like to express my gratitude to my doctoral supervisor Prof. Dr. Hans-Gerd Löhmannsröben for his support and for giving me the opportunity to do my doctorate in chemistry. My special thanks is directed to the mentor of the group “Biomimetic Materials and Systems” Prof. Dr. Frieder W. Scheller who acted as a scientific supervisor. I am thankful for many fruitful discussions, interesting new aspects and many corrections of my written thesis or manuscripts. Substantial guidance has also been given by Prof. Dr. Dennis G. Hall, University of Alberta, Edmonton. He gave me the chance to learn the chemistry of “boronic acids” in his lab and supported my work also after my return to Germany.
    [Show full text]
  • Copper in Cross-Coupling Reactions Copper in Cross-Coupling Reactions
    Mechanistic Studies in Copper Catalysis Jen Alleva May 1st 2013 Timeline of Achievements in Copper Chemistry General Historical Overview first cross-couplings Ullmann–Goldberg 1869 Glaser 1903 Glaser, C. Ann. D. Chemie U. Pharm, 1869, 2, 137–171 Timeline of Achievements in Copper Chemistry General Historical Overview first cross-couplings Ullmann–Goldberg 1869 Glaser 1903 Ullman, F. Ber. 1903, 36, 2382–2384 Goldberg, I. Ber. 1906, 39, 1691–1692 Timeline of Achievements in Copper Chemistry General Historical Overview first cross-couplings Ullmann–Goldberg 1869 1923 1952 Glaser 1903 Reich Gilman synthesis of first copper organometallic reagents Gilman, H.; Jones, R. G.; Woods, L. A. J. Org. Chem, 1952, 17, 1630–1634 Timeline of Achievements in Copper Chemistry General Historical Overview first cross-couplings "Click" Chemistry Ullmann–Goldberg Huisgen 1869 1923 1952 2001 Glaser 1903 Reich Gilman 1961 Sharpless synthesis of first copper organometallic reagents Huisgen, R. Proc. Chem Soc., 1961, 357–396 Timeline of Achievements in Copper Chemistry General Historical Overview first cross-couplings "Click" Chemistry Ullmann–Goldberg Huisgen 1869 1923 1952 1998 2001 Glaser 1903 Reich Gilman 1961 Sharpless synthesis of first copper Chan-Evans-Lam organometallic reagents Cu C–N couplings Huisgen, R. Proc. Chem Soc., 1961, 357–396 Copper in Cross-Coupling Reactions Copper in Cross-Coupling Reactions RO OR B X Nu X O X HN O X = N, O, S X = halide nucleophile X = halide oxidative coupling standard cross-coupling oxidative coupling X Nu X Chan-Evans-Lam Ullmann-Goldberg "Aromatic Glaser-Hay" Electronic Properties of Copper E1/2= 0.16V E1/2= 2.4V CuI CuII CuIII d10 d9 d8, metal cation isoelectronic with isoelectronic with Ni(0) Pd(II) * Vs.
    [Show full text]
  • Solubility of Phenylboronic Acid and Its Cyclic Esters in Organic Solvents
    Journal of Solution Chemistry (2020) 49:814–824 https://doi.org/10.1007/s10953-020-00988-y Solubility of Phenylboronic Acid and its Cyclic Esters in Organic Solvents Paweł Leszczyński1 · Tadeusz Hofman1 · Andrzej Sporzyński1 Received: 20 December 2019 / Accepted: 3 March 2020 / Published online: 6 June 2020 © The Author(s) 2020 Abstract The solubilities of phenylboronic acid, its pinacol ester and azaester in organic solvents (chloroform, 3-pentanone, acetone, dipropyl ether and methylcyclohexane) have been determined experimentally by a dynamic method, in which the disappearance of turbid- ity was determined by measuring of light intensity using a luminance probe. Phenylbo- ronic acid has high solubility in ether and ketones, moderate in chloroform and very low in hydrocarbon. Pinacol ester and azaester show better solubility than the parent acid in all tested solvents. For pinacol ester diferences between particular solvents are small, while for azaester the diferences are signifcant. For both esters the highest solubility is observed in chloroform and the lowest in the hydrocarbon. The results have been correlated by the Wilson, NRTL and Redlich–Kister equations. For the phenylboronic acid better correlation of the data is obtained by polynomials in comparison with the above equations. It is con- nected with additional acid-anhydride equilibrium in the system. The infuence of polarity of the solvents on the solubility is discussed. Keywords Boronic acids · Boronic esters · Solubility · Redlich–Kister equation · Wilson equation · NRTL equation 1 Introduction Arylboronic acids and their derivatives are an important group of compounds due to their broad applications in organic synthesis, catalysis, supramolecular chemistry, and materi- als engineering [1–4].
    [Show full text]
  • University of California Santa Cruz Synthesis of Boronic
    UNIVERSITY OF CALIFORNIA SANTA CRUZ SYNTHESIS OF BORONIC ACIDS AND ESTERS FROM PINACOLBORANE AND AMINOBORANE UNDER AMBIENT MAGNESIUM-, IODINE-, AND ZINC-MEDIATED CONDITIONS A dissertation submitted in partial satisfaction of the requirements for the degree of DOCTOR OF PHILOSOPHY in CHEMISTRY AND BIOCHEMISTRY by Christopher Lee William Murphy December 2016 The Dissertation of Christopher L. W. Murphy is approved: ______________________________ Professor Bakthan Singaram, Advisor ______________________________ Professor Rebecca Braslau, Chair ______________________________ Professor Scott Lokey ______________________________ Tyrus Miller Vice Provost and Dean of Graduate Studies Copyright © by Christopher L. W. Murphy 2016 TABLE OF CONTENTS LIST OF FIGURES vii LIST OF SCHEMES x LIST OF TABLE xix ABSTRACT xxi CHAPTER 1. Review of Boronic Acid and Ester Synthesis and their Applications in Organic Chemistry 1 1.1 Introduction 2 1.1.1 Boron and Boranes 2 1.1.2 Boronic Acids and Esters 3 1.1.3 Structural, Electronic, and Acidic Properties 4 1.1.4 Analysis of Boronic Acids and Esters 11 1.2 Synthesis of Boronic Acids and Esters 12 1.2.1 Early Synthetic Methods of Boronic Acids and Esters 13 1.2.2 Miyaura Borylation 16 1.2.3 Synthesis of Boronic acids via Aminoboranes 18 1.2.4 C-H Activation 19 1.2.5 Synthesis of Boronic Acids and Esters through Transition Metals 21 1.3 Applications of Boronic Acids and Esters 23 iii 1.3.1 Suzuki Coupling 23 1.3.2 Chan-Lam Coupling 35 1.3.3 Boronic Acids as Saccharide Sensors 41 1.4 Conclusion 46 1.5 Thesis Outline 47 1.6 References 48 CHAPTER 2.
    [Show full text]