Borinic Acids As New Fast-Responsive Triggers For
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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 -
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. -
RSC Advances PAPER
View Article Online / Journal Homepage / Table of Contents for this issue RSC Advances Dynamic Article Links Cite this: RSC Advances, 2012, 2, 3968–3977 www.rsc.org/advances PAPER Palladium nanoshells coated with self-assembled monolayers and their catalytic properties Jun-Hyun Kim,*a Joon-Seo Park,b Hae-Won Chung,c Brett W. Bootea and T. Randall Lee*c Received 13th October 2011, Accepted 6th February 2012 DOI: 10.1039/c2ra00883a This report describes the preparation and characterization of palladium nanoshells protected with alkanethiol self-assembled monolayers (SAMs) and their application as efficient catalysts. Monodispersed silica core particles (y100 nm in diameter) were prepared and coated with a thin layer of palladium (y20 nm in thickness). Subsequently, the palladium nanoshells were treated with two separate alkanethiol adsorbates having different alkyl chain lengths: dodecanethiol (C12SH) and hexadecanethiol (C16SH). The optical properties, morphology, and chemical structure/composition of these nanoshells were thoroughly examined by ultraviolet-visible spectroscopy, field-emission scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and Fourier-transform infrared spectroscopy. Additional studies revealed that these SAM-coated palladium nanoshells possessed enhanced colloidal stability in nonpolar solvents and in the solid state. Further, palladium nanoshells modified with C16SH SAM coatings were employed in the Suzuki coupling of phenylboronic acid with iodobenzene in organic solvents. Notably, these SAM-coated nanoshells afforded a greater conversion yield than that of related bare palladium nanoshells. Downloaded on 19 February 2013 Introduction palladium nanoparticles as catalysts depend largely on their size, shape, surrounding medium, and dispersion ability in organic The controlled fabrication of nanoscale metallic particles offers the solvents, which facilitates their manipulation and incorporation 1–5 opportunity to develop novel catalysts. -
C7sc03595k1.Pdf
Electronic Supplementary Material (ESI) for Chemical Science. This journal is © The Royal Society of Chemistry 2018 Mechanistic insights into boron-catalysed direct amidation reactions Sergey Arkhipenko,a Marco T. Sabatini,b Andrei Batsanov,a Valerija Karaluka,b Tom D. Sheppard,b Henry S. Rzepac and Andrew Whitinga* aCentre for Sustainable Chemical Processes, Department of Chemistry, Durham University, Science Site, South Road, Durham, DH1 3LE, UK. Email: [email protected] bDepartment of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ, UK. cDepartment of Chemistry, Imperial College London, South Kensington Campus, London, SW7 2AZ, UK. Contents Page 1. General experimental 2 2. Synthetic procedures and compound characterisation§ 2.A. Reaction of monomeric acyloxyboron species with amines 3 2.B. Synthesis of borinic acids and studies of their interactions 6 with amines and carboxylic acids 2.C. Interactions of boronic acids with amines and carboxylic acids 10 2.D. Interaction of B2O3 and B(OH)3 with amines and carboxylic acids 21 2.E. Kinetic studies 22 3. Tabulated summary of spectroscopic data 29 4. X-ray crystallographic information# 30 5. References 36 §Note that all NMR data and .cif crystallographic data is available for download from site: DOI: 10.14469/hpc/1620 and sub-collections therein. GENERAL EXPERIMENTAL All starting materials and solvents were obtained commercially from standard chemical suppliers and were used as received unless otherwise stated. Dry solvents were prepared using the Innovative Technology Inc. solvent purification system, or dried by known methods, including standing over 4 Å molecular sieves for 24 h in the case of toluene and CDCl3. -
Electronic Supporting Information
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is © The Royal Society of Chemistry 2017 Electronic Supporting Information for Ratiometric Electrochemical Detection of Hydrogen Peroxide and Glucose by Sean Goggins,a* Ellen A. Apsey,a Mary F. Mahona and Christopher G. Frosta a Department of Chemistry, 1 South, University of Bath, Claverton Down, Bath, BA2 7AY, UK * Corresponding author: [email protected] Contents General Information ................................................................................................................................... S4 Instruments and Analysis ........................................................................................................................ S4 Materials ................................................................................................................................................. S4 Chemicals ................................................................................................................................................ S4 Electrochemistry ..................................................................................................................................... S5 Diagnostic Assays .................................................................................................................................... S5 Synthetic Routes ......................................................................................................................................... S6 Synthetic Route -
Diyl Bis(Phenyl-Methanone) Via Carbonylative Coupling
Asian Journal of Chemistry; Vol. 25, No. 15 (2013), 8611-8613 http://dx.doi.org/10.14233/ajchem.2013.14863 Synthesis of Biphenyl- 4,4'-Diyl bis(phenyl-methanone) via Carbonylative Coupling 1,* 2 1,* DO-HUN LEE , JUNG-TAI HAHN and DAI-IL JUNG 1Department of Chemistry, Dong-A University, Busan 604 714, Republic of Korea 2Department of Beautycare, Youngdong University, Youngdong 370 701, Republic of Korea *Corresponding authors: Tel: +82 51 2007249; +82 51 2001053; E-mail: [email protected]; [email protected] (Received: 23 November 2012; Accepted: 26 August 2013) AJC-14008 Luminescent meterials have a major technological role for human kind in the form of application such as organic and inorganic light emitters for flat panel and flexible displays such as plasma displays, LCD displays and OLED displays. To develop a luminescent material with high colour purity, luminous efficiency and stability, we synthesized diketone by carbonylative Suzuki coupling in the presence of Pd(NHC) (NHC = N-heterocyclic carbene) complex as the catalyst. Carbonylative coupling of 4,42-diiodobiphenyl and phenylboronic acid was investigated to study in detail the catalytic ability of the Pd(NHC) complex. Reactions were carried out using both CO and metal carbonyls. Bis-(1,3-dihydro-1,3-dimethyl-2H-imidazol-2-ylidene) diiodo palladium was used as the catalytic complex. Reaction products biphenyl-4,4'-diyl bis(phenyl methanone) 3 and (4'-iodobiphenyl-4-yl)(phenyl)methanone 4 were obtained as a result of CO insertion into the palladium(II)-aryl bond. However, when pyridine-4-yl boronic acid was used in place of phenylboronic acid as the starting reagent, synthetic reaction yielding 3 and 4 were found not to occur. -
Supporting Information for Boronic Acid–DMAPO Cooperative Catalysis for Dehydrative Condensation Between Carboxylic Acids and Amines
Electronic Supplementary Material (ESI) for Chemical Science. This journal is © The Royal Society of Chemistry 2015 Supporting Information for Boronic Acid–DMAPO Cooperative Catalysis for Dehydrative Condensation between Carboxylic Acids and Amines Kazuaki Ishihara*†‡ and Yanhui Lu† †Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan ‡Japan Science and Technology (JST), CREST, Japan E-mail: [email protected] Contents General Methods……………………………………………………………….….……..……S2 Detailed Synthetic Procedures and Characterization of the Products…………….….…....S2 Inert Species 9…………………..………………………………….………………………....S11 Control Experiments for the Chemoselective Dehydrative Condensation of Unsaturated Carboxylic Acids………………………………………………….…....S15 References…………………………………………………………………………………….S17 1H and 13C NMR Charts of New Compounds……………………………………….……..S18 S1 Experimental section General Methods. IR spectra were recorded on a JASCO FT/IR-460 plus spectrometer. 1H NMR spectra were measured on a JEOL ECS-400 spectrometer (400 MHz) at ambient temperature. Data were recorded as follows: chemical shift in ppm from internal tetramethysilane on the δ scale, multiplicity (s = singlet; d = doublet; t = triplet; m = multiplet), coupling constant (Hz), and integration. 13C NMR spectra were measured on a JEOL ECS-400 (100 MHz). Chemical shifts were recorded in ppm from the solvent resonance employed as the internal standard (CDCl3 at 77.0 11 ppm). B NMR spectra were taken on a JEOL ECS-400 (128 MHz) spectrometer using B(OMe)3 as an external reference. Analytical HPLC was performed on a Shimadzu Model LC-10AD instrument coupled diode array-detector SPD-MA-10A-VP using a column of Daicel CHIRALCEL OD-H (4.6 # 250 mm). Optical rotations were measured on a RUDOLPH AUTOPOL IV digital polarimeter. -
Palladium-Catalyzed Asymmetric Conjugate Addition of Arylboronic Acids to Heterocyclic Acceptors
NIH Public Access Author Manuscript Chemistry. Author manuscript; available in PMC 2014 January 02. NIH-PA Author ManuscriptPublished NIH-PA Author Manuscript in final edited NIH-PA Author Manuscript form as: Chemistry. 2013 January 2; 19(1): 74–77. doi:10.1002/chem.201203643. Palladium-Catalyzed Asymmetric Conjugate Addition of Arylboronic Acids to Heterocyclic Acceptors Jeffrey C. Holder#, Dr. Alexander N. Marziale#, Dr. Michele Gatti, Bin Mao, and Prof. Brian M. Stoltz Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E California Blvd, MC 101-20, Pasadena, CA 91125 (USA) Keywords Heterocycles; Conjugate Addition; Asymmetric Catalysis; Palladium; Arylboronic Acids Palladium-catalyzed asymmetric conjugate additions are an increasingly versatile class of enantioselective reactions that allow for stereoselective alkylation and arylation of α,β- unsaturated conjugate acceptors.[1] These processes often utilize easily-handled, air- and water-stable boron nucleophiles that render these reactions highly tolerant of oxygen and moisture.[2] Recently, our group disclosed the asymmetric conjugate addition of arylboronic acids to cyclic enones facilitated by a palladium catalyst derived in situ from palladium(II) trifluoroacetate and a chiral pyridinooxazoline (PyOX) ligand (5).[3] Notably, our catalyst system was generally applicable for 5-, 6-, and 7-membered carbocyclic enones. The numerous advantages of this system encouraged us to seek application to heterocyclic molecules, in order to demonstrate the broad utility of this reaction for the synthesis of pharmaceutically relevant molecules. Herein, we report the first general enantioselective conjugate addition of arylboronic acids to heterocyclic conjugate acceptors derived from chromones and 4-quinolones utilizing the Pd/PyOX catalyst system. -
Polymer Substrates for Fiber-Optic Chemical Sensors
University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Winter 1992 Polymer substrates for fiber-optic chemical sensors Amy Elizabeth Straub University of New Hampshire, Durham Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation Straub, Amy Elizabeth, "Polymer substrates for fiber-optic chemical sensors" (1992). Doctoral Dissertations. 1718. https://scholars.unh.edu/dissertation/1718 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. INFORMATION TO USERS This manuscript has been reproduced from the microfilm master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand corner and continuing from left to right in equal sections with small overlaps. -
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. -
1 Rhodium- and Palladium-Catalyzed Asymmetric Conjugate Additions Guillaume Berthon and Tamio Hayashi
1 1 Rhodium- and Palladium-Catalyzed Asymmetric Conjugate Additions Guillaume Berthon and Tamio Hayashi 1.1 Introduction Since the seminal report by Uemura [1] in 1995 for palladium, and by Miyaura in 1997 for rhodium [2], the late transition metal-catalyzed conjugate addition of organoboron reagents to activated alkenes has emerged as one of the most functional group-tolerant and reliable carbon–carbon bond-forming processes. The maturity of this methodology is such that it has become an ideal testing ground for new ligand concepts and design, as will be illustrated throughout this chapter. A true statement to the robustness of this process is the application of Rh-catalyzed enantioselective conjugate addition (ECA) on a kilogram-scale for the manufacture of advanced pharmaceutical ingredients, and its use as a key step in the synthesis of complex natural products [3–5]. In this chapter, an overview will be provided – spanning from 2003 to mid-2009 – of the developments in the field of rhodium- and palladium-catalyzed ECA of organometallic reagents (B, Si, Zn, and Ti) to activated alkenes. The chapter is not intended to be comprehensive, and will include only selected examples of this powerful methodology. For more in-depth and comprehensive accounts, the reader should consult a number of excellent reviews that are available on this subject [6–16]. 1.2 Rh-Catalyzed ECA of Organoboron Reagents This section will include details of the state of the art for the rhodium-catalyzed ECA of organoboron reagents to activated olefins. Special emphasis will be placed on α,β-unsaturated ketones, as this substrate class has attracted the most attention and undergone thorough investigation with a plethora of different ligand systems. -
Synthesis and Applications a Di
UNIVERSITY OF CALIFORNIA Los Angeles Trehalose Polymers and Ruthenium-Catalyzed Polymerizations: Synthesis and Applications A dissertation submitted in partial satisfaction of the requirements for the degree Doctor of Philosophy in Chemistry by Jeong Hoon Ko 2018 © Copyright by Jeong Hoon Ko 2018 ABSTRACT OF THE DISSERTATION Trehalose Polymers and Ruthenium-Catalyzed Polymerizations: Synthesis and Applications by Jeong Hoon Ko Doctor of Philosophy in Chemistry University of California, Los Angeles, 2018 Professor Heather D. Maynard, Chair Since the definition of polymers as covalently linked macromolecules by Hermann Staudinger in 1920, polymers have become indispensable components of our society as industrial materials, consumer products, and medical devices only to name a few applications. This explosive growth of polymer use in the past century, referred to as “The Plastics Revolution”, was driven by research into polymerization techniques for various monomer types appropriate for the desired application. The past two decades have been marked by the development of controlled polymerization methods in addition to advances in new chemical reactions that are highly efficient. The combination of controlled polymerization techniques with methodologies in other fields of organic chemistry is expected to lead to a second plastics revolution, enabling polymers to further enhance our society by materials with new applications. The first five chapters of this dissertation are related to the use of controlled radical polymerization in combination with methods for protein-polymer conjugation, carbohydrate ii synthesis, and click chemistry to enhance the properties of protein drugs. Proteins have many desirable traits for therapeutic use, but their potential has yet to be fully realized due to their low physical stability and rapid clearance from the body by multiple elimination pathways.