Activation of Silicon Bonds by Fluoride Ion in the Organic Synthesis in the New Millennium: a Review
Total Page:16
File Type:pdf, Size:1020Kb
Load more
Recommended publications
-
Contemporary Organosilicon Chemistry
Contemporary organosilicon chemistry Edited by Steve Marsden Generated on 05 October 2021, 02:13 Imprint Beilstein Journal of Organic Chemistry www.bjoc.org ISSN 1860-5397 Email: [email protected] The Beilstein Journal of Organic Chemistry is published by the Beilstein-Institut zur Förderung der Chemischen Wissenschaften. This thematic issue, published in the Beilstein Beilstein-Institut zur Förderung der Journal of Organic Chemistry, is copyright the Chemischen Wissenschaften Beilstein-Institut zur Förderung der Chemischen Trakehner Straße 7–9 Wissenschaften. The copyright of the individual 60487 Frankfurt am Main articles in this document is the property of their Germany respective authors, subject to a Creative www.beilstein-institut.de Commons Attribution (CC-BY) license. Contemporary organosilicon chemistry Steve Marsden Editorial Open Access Address: Beilstein Journal of Organic Chemistry 2007, 3, No. 4. School of Chemistry, University of Leeds, Leeds LS2 9JT, UK doi:10.1186/1860-5397-3-4 Email: Received: 06 February 2007 Steve Marsden - [email protected] Accepted: 08 February 2007 Published: 08 February 2007 © 2007 Marsden; licensee Beilstein-Institut License and terms: see end of document. Abstract Editorial for the Thematic Series on Contemporary Organosilicon Chemistry. The field of organosilicon chemistry has a rich and varied the 1990s, and equivalent to the number appearing in the much history, and has long since made the progression from chemical longer established field of organoboron chemistry -
Nigam Prasad Rath Research Professor
Nigam Prasad Rath Research Professor Department of Chemistry and Biochemistry University of Missouri - St. Louis One University Boulevard St. Louis, MO 63121. E-mail: [email protected] Phone: 314-516-5333 FAX: 314-516-5342 Education : B. Sc.(Honors) : 1st Class Honors in Chemistry with Distinction, Berhampur University, Berhampur, India, 1977. M. Sc. (Chemistry): 1st Class, Berhampur University, Berhampur, India, 1979. Ph. D. (Chemistry): Oklahoma State University, Stillwater, OK, USA, 1985. Professional Experience: Research Professor , Department of Chemistry and Biochemistry, University of Missouri, St. Louis, MO, 2004 to present. Research Associate Professor , Department of Chemistry, University of Missouri, St. Louis, MO, 1997 to 2004. Research Assistant Professor , Department of Chemistry, University of Missouri, St. Louis, MO, 1989 to 1996. Assistant Faculty Fellow , Department of Chemistry, University of Notre Dame, Notre Dame, IN 1987 to 1989. Post Doctoral Research Associate , Department of Chemistry, University of Notre Dame, Notre Dame, IN 1986-87. Graduate Assistant , Department of Chemistry, Oklahoma State University, Stillwater, OK 1982 to 1985. Junior Research Fellow (CSIR) , Department of Chemistry, Indian Institute of Technology, Kharagpur, India, 1981-82. Junior Research Fellow , Department of Chemistry, Indian Institute of Technology, Kanpur, India, 1979 to 1981. 2 Professional Positions: Visiting Scientist, Monsanto Corporate Research, Chesterfield, MO, 1992 to 1994. Scientific Consultant, Regional Research Laboratory, Trivandrum, India, 1992 to present. Assistant Professor, Evening College, University of Missouri, St. Louis, 1992 to 2000. Research Mentor, Engelmann Mathematics and Science Institute, University of Missouri, St. Louis, 1990 to 1998. Research Mentor, NSF STARS Program, University of Missouri, St. Louis, 1999 to present. Honors and Awards: National Merit Scholarship, India, 1977-79. -
Silylation and Characterization of of Piroxicam with Some Silylating Reagents
Silylation and characterization of of piroxicam with some silylating reagents Mohammad Galehassadi ( [email protected] ) Azarbaijan Shahid Madani University Somayeh Jodeiri Azarbaijan Shahid Madani University Research Article Keywords: Piroxicam, Silyl ether, Organosilicon, Drug delivery, Lipophilic Posted Date: March 22nd, 2021 DOI: https://doi.org/10.21203/rs.3.rs-345479/v1 License: This work is licensed under a Creative Commons Attribution 4.0 International License. Read Full License Silylation and characterization of of piroxicam with some silylating reagents Mohammad. galehassadi, *, a Somayeh Jodeiri a Department of Chemistry, Azarbaijan Shahid Madani University, Tabriz, Iran; e-mail: Email:[email protected] Tel: +984134327541 Mobile: +989144055400 Abstract: In this work, we synthesized some organosilicon derivatives of piroxicam. Due to the some properties of organosilicon compounds, including increased lipophilicity and thermal stabilization and prodrug for drugs, some silyl ethers of this drug were synthesized and characterized..Increasing of the lipophilic properties of this drug can be very important in the rate of absorption and its effectiveness. Graphic abstract: Keywords: Piroxicam, Silyl ether, Organosilicon, Drug delivery, Lipophilic 1.Introduction: Piroxicam is a painkiller and its main use is to reduce or stop pain. In osteoarthritis, this drug has anti-inflammatory effects. This drug is used to treat many diseases such as headache and toothache, leg pain and piroxicam reduces the production of prostaglandins by controlling cyclooxygenase, thus showing its effectiveness in reducing and eliminating pain. It is also used to relieve joint, bone and muscle pain. It is even used to control gout and menstrual cramps. It binds to a large amount of protein and is metabolized in the liver and then excreted in the urine. -
Silyl Ketone Chemistry. Preparation and Reactions of Silyl Allenol Ethers. Diels-Alder Reactions of Siloxy Vinylallenes Leading to Sesquiterpenes2
J. Am. Chem. SOC.1986, 108, 7791-7800 7791 pyrany1oxy)dodecanoic acid, 1.38 1 g (3.15 mmol) of GPC-CdCIz, 0.854 product mixture was then filtered and concentrated under reduced g (7.0 mmol) of 4-(dimethylamino)pyridine, and 1.648 g (8.0 mmol) of pressure. The residue was dissolved in 5 mL of solvent B and passed dicyclohexylcarbodiimide was suspended in 15 mL of dry dichloro- through a 1.2 X 1.5 cm AG MP-50 cation-exchange column in order to methane and stirred under nitrogen in the dark for 40 h. After removal remove 4-(dimethylamino)pyridine. The filtrate was concentrated under of solvent in vacuo, the residue was dissolved in 50 mL of CH30H/H20 reduced pressure, dissolved in a minimum volume of absolute ethanol, (95/5, v/v) and stirred in the presence of 8.0 g of AG MP-50 (23 OC, and then concentrated again. Chromatographic purification of the res- 2 h) to allow for complete deprotection of the hydroxyl groups (monitored idue on a silica gel column (0.9 X 6 cm), eluting first with solvent A and by thin-layer chromatography)." The resin was then removed by fil- then with solvent C (compound 1 elutes on silica as a single yellow band), tration and the solution concentrated under reduced pressure. The crude afforded, after drying [IO h, 22 OC (0.05 mm)], 0.055 g (90%) of 1 as product (2.75 g). obtained after drying [12 h, 23 OC (0.05 mm)], was a yellow solid: R 0.45 (solvent C); IR (KBr) ucz0 1732, uN(cH3)3 970, then subjected to chromatographic purification by using a 30-g (4 X 4 1050, 1090cm-'; I' H NMR (CDCI,) 6 1.25 (s 28 H, CH2), 1.40-2.05 (m, cm) silica gel column, eluting with solvents A and C, to yield 0.990 g 20 H, lipoic-CH,, CH2CH20,CH2CH,C02), 2.3 (t. -
The Synthesis of N-Substituted Ferrocenes and C–H Activation
View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Publikationsserver der RWTH Aachen University The Synthesis of N -Substituted Ferrocenes and C–H Activation Towards the Synthesis of Organosilanols Salih Oz¸cubuk¸cu¨ Dissertation The Synthesis of N -Substituted Ferrocenes and C–H Activation Towards the Synthesis of Organosilanols Von der Fakult¨at f¨ur Mathematik, Informatik und Naturwissenschaften der Rheinisch-Westf¨alischen Technischen Hochschule Aachen zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften genehmigte Dissertation vorgelegt von Master of Science Salih Oz¸cubuk¸cu¨ aus Gaziantep (T¨urkei) Berichter: Universit¨atsprofessor Dr. Carsten Bolm Universit¨atsprofessor Dr. Dieter Enders Tag der m¨undlichen Pr¨ufung: 22 Januar 2007 Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verf¨ugbar. For everybody The work presented in this thesis was carried out at the Institute of Organic Chemistry of the RWTH-Aachen University, under the supervision of Prof. Dr. Carsten Bolm between January 2003 and July 2006. I would like to thank Prof. Dr. Carsten Bolm for giving me the opportunity to work on this exciting research topic, excellent conditions and support in his research group. I would like to thank Prof. Dr. Dieter Enders for his kind assumption of the co-reference. Parts of this work have already been published or submitted: ’Organosilanols as Catalysts in Asymmetric Aryl Transfer Reactions’ Oz¸cubuk¸cu,¨ S.; Schmidt, F.; Bolm, C. Org. Lett. 2005, 7, 1407. (This article has been highlighted in Synfact 2005, 0, 41.) ’A General and Efficient Synthesis of Nitrogen-Substituted Ferrocenes’ Oz¸cubuk¸cu,¨ S.; Scmitt, E.; Leifert, A.; Bolm, C.; Synthesis 2007, 389. -
Copyrighted Material
525 Index a alcohol racemization 356, 357 acetophenone 50–53, 293, 344, 348, 443 alkali metals 398 acetoxycyclization, of 1,6-enyne 76 alkaline earth metals 398 acetylacetone 48 N-alkenyl-substituted N,S-HC ligands 349 A3 coupling reactions 231, 232 3-alkyl-3-aryloxindoles 58 acrylonitriles 69, 211, 212, 310, 348 alkyl bis(trimethylsilyloxy) methyl silanes 122 activation period 123–125 – Tamao-Kumada oxidation of 122 active species 123 2-alkylpyrrolidyl-derived formamidinium acyclic alkane 62 precursors 516 acyclic aminocarbenes 499 alkyl silyl-fluorides 209 – ligands 503 alkyl-substituted esters 210 – metalation routes 500 N-alkyl substituted NHC class 119 acyclic aminocarbene species 499 alkynes acyclic carbene chemistry 500, 516–520 – boration of 225 acyclic carbene complexes – borocarboxylation 233, 234 – in Suzuki–Miyaura crosscoupling 505 – hydrocarboxylation 234, 235 acyclic carbene–metal complexes 505 – metal-catalyzed hydrosilylation of 132 acyclic carbenes – semihydrogenation 232, 233 – characteristic feature of 503 allenes 77 – donor abilities 502 – synthesis, mechanisms 203 – ligands 502 3-allyl-3-aryl oxindoles 60 –– decomposition routes 504 allylbenzene 345 –– donor ability 502, 503 – cross-metathesis (CM) reactions of –– metalation routes of 500 510 –– structural properties 503 allylic alkylations 509 – stabilized, by lateral enamines 518 allylic benzimidate acyclic carbone ligand 519 – aza-Claisen rearrangement of 514 – in gold-catalyzed rearrangements 520 allylic substitution 220 acyclic diaminocarbenes (ADCs) 4, 5, 499 -
Organosilicon Compounds for Organic Synthesis
Organosilicon Compounds For Organic Synthesis Introduction Recently, the use of organosilicon compounds in organic chemistry has become an increasingly important field. As such, Shin-Etsu Chemical has been a key supplier for many silylating agents currently in use while also searching for and developing new and useful organosilicon compounds. This booklet introduces several newly developed silylating agents and organosilicon compounds, including references for their application. SILYLATING AGENTS General Definition Silylating agents are reagents that are used to replace the active hydrogen of a chemical species with a silyl group (-Si RR'R"). For example,functional groups such as -OH, -COOH, -NH2, -CONH2, and -SH are converted to -OSiRR'R", -COOSiRR'R", -NHSiRR'R", CONHSiRR'R", and -SSiRR'R",respectively. Purpose In general, the replacement of active hydrogens significantly decreases the reactivity of a functional group and dramatically reduces polar interactions such as hydrogen bonding. These replacements can be carried out for many specific reasons, but typically fall under one or more of the following objectives: (1) Protecting a reactive functional group during one or more chemical reactions (2) Improving the selectivity of a chemical reaction (3) Improving stability during distillation (4) Improving solubility in polar and/or non-polar solvents (5) Increasing volatility by reducing or eliminating hydrogen-bonding How To Select? The most common silylating agents used on an industrial scale are listed in Table I. Reactivity, type of by-product, price, and availability are often important factors that must be considered when the synthetic process is developed. Another important factor to be considered, the stability of the resultant silylated functional group, is largely determined by the combined steric bulk of the alkyl groups attached to silicon (R, R', and R"). -
Photoredox-Catalyzed Silyldifluoromethylation of Silyl Enol Ethers
Photoredox-catalyzed silyldifluoromethylation of silyl enol ethers Vyacheslav I. Supranovich, Vitalij V. Levin and Alexander D. Dilman* Letter Open Access Address: Beilstein J. Org. Chem. 2020, 16, 1550–1553. N. D. Zelinsky Institute of Organic Chemistry, Leninsky prosp. 47, doi:10.3762/bjoc.16.126 119991 Moscow, Russian Federation Received: 15 April 2020 Email: Accepted: 15 June 2020 Alexander D. Dilman* - [email protected] Published: 29 June 2020 * Corresponding author This article is part of the thematic issue "Organo-fluorine chemistry V". Keywords: Guest Editor: D. O'Hagan difluoroalkylation; organofluorine compounds; photocatalysis; radical addition; silicon reagents © 2020 Supranovich et al.; licensee Beilstein-Institut. License and terms: see end of document. Abstract A method for the light-mediated fluoroalkylation of silyl enol ethers with (bromodifluoromethyl)trimethylsilane followed by a reduction of the primary products with sodium borohydride is described. An 18 W, 375 nm LED was used as the light source. The reaction is performed in the presence of a gold photocatalyst, which effects the generation of a (trimethylsilyl)difluoromethyl radical via cleavage of the carbon–bromine bond. Findings Fluorinated silicon reagents have found widespread use for the to Lewis bases and accordingly it was used as a precursor of introduction of fluorinated fragments [1-5]. Typically, these difluorocarbene, which can react with enol ethers [19,20] reagents work under strongly basic conditions required to acti- (Scheme 1). We showed that this silane could be involved in the vate inert C–Si bonds with the generation of carbanionic radical chain hydrofluoroalkylation of electron-deficient species. On the other hand, radical reactions offer different syn- alkenes, using a boron hydride as a source of hydrogen [21]. -
Bonding and Structure of Disilenes and Related Unsaturated Group-14 Element Compounds
No. 5] Proc. Jpn. Acad., Ser. B 88 (2012) 167 Review Bonding and structure of disilenes and related unsaturated group-14 element compounds † By Mitsuo KIRA*1, (Communicated by Hitosi NOZAKI, M.J.A.) Abstract: Structure and properties of silicon-silicon doubly bonded compounds (disilenes) are shown to be remarkably different from those of alkenes. X-Ray structural analysis of a series of acyclic tetrakis(trialkylsilyl)disilenes has shown that the geometry of these disilenes is quite flexible, and planar, twist or trans-bent depending on the bulkiness and shape of the trialkylsilyl substituents. Thermal and photochemical interconversion between a cyclotetrasilene and the corresponding bicyclo[1.1.0]tetrasilane occurs via either 1,2-silyl migration or a concerted electrocyclic reaction depending on the ring substituents without intermediacy of the corresponding tetrasila-1,3-diene. Theoretical and spectroscopic studies of a stable spiropentasiladiene have revealed a unique feature of the spiroconjugation in this system. Starting with a stable dialkylsilylene, a number of elaborated disilenes including trisilaallene and its germanium congeners are synthesized. Unlike carbon allenes, the trisilaallene has remarkably bent and fluxional geometry, suggesting the importance of the :-<* orbital mixing. 14-Electron three-coordinate disilene- palladium complexes are found to have much stronger :-complex character than related 16-electron tetracoordinate complexes. Keywords: silicon, germanium, double bond, synthesis, structure, theoretical calculations -
View a Complete List of Ph.D Degrees
1913 1. CLARK, Clinton Willard. (Title not Available). 2. CLARK, Hugh. An Improved Method for the Manufacture of Hydrogen and Lamp Black. 3. CORLISS, Harry Percival. The Distribution of Colloidal Arsenic Trisulfide between the Phases in the System Ether, Water, and Alcohol. 4. PRATT, Lester Albert. Studies in the Field of Petroleum. 5. SHIVELY, Robert Rex. A Study of Magnesia Cements. 1914 6. UHLINGER, Roy H. The Formation of Utilizable Products from Natural Gas. 1915 7. DUNPHY, Raymond Augustine. Theory of Distillation and the Laws of Henry and Raoult. 8. LIEBOVITZ, Sidney. Study of Dynamics of Esterification. 9. MORTON, Harold Arthur. Study of the Specific Rotatory Power of Organic Substances in Solution. 10. WITT, Joshua Chitwood. Oxidation and Reduction Without the Addition of Acid. I. The Reaction between Ferrous Sulfate and Potassium Dichromate. II. The Reaction Between Stanous Chloride and Potassium Dichromate. (Neidle) 1917 11. COLEMAN, Arthur Bert. Tetraiodofluorescein, Tetraiodoeosin, Tetraiodoerythrosin and Some of Their Derivatives. (Pratt) 12. MILLER, Rolla Woods. On the Mechanism of the Potassium Chlorate-Manganese Dioxide Reaction. 13. PERKINS, Granville Akers. Phthalic Anhydride and Some of Its Derivatives. (Pratt) 14. SHUPP, Asher Franklin. Phenoltetraiodophthalein and Some of Its Derivatives. (Pratt) 1919 15. CURME, Henry R. Butadiine (Diacetylene). II. Analysis of Gas Mixtures by Distillation at Low Temperatures and Low Pressures. III. The Precise Analytical Determination of Acetylene, Ethylene, and Methyl Acetylene in Hydrocarbon Gas Mixtures. 16. DROGIN, Isaac. The Effect of Potassium Chloride on the Inversion of Cane Sugar by Formic Acid. 17. YOUNG, Charles Otis. Tetrabromophthalic Acid and Its Condensation with Some Primary Amines. 1 1920 18. -
The Development of New Organotin Reagents for Organic Synthesis
THE DEVELOPMENT OF NEW ORGANOTIN REAGENTS FOR ORGANIC SYNTHESIS by Chee-Kiang Lim S.B. Chemistry, Massachusetts Institute of Technology (1995) Submitted to the Department of Chemistry in Partial Fulfillment of the Requirements for the Degree of MASTER OF SCIENCE IN CHEMISTRY at the Massachusetts Institute of Technology June 1995 © Chee-Kiang Lim, 1995 All rights reserved The author hereby grants to MIT permission to reproduce and to distribute publicly paper and electronic copies of this thesis d, ument in whole or in part. lX Signature of Author - - I Department of Chemistry May 10, 1995 Certified by - Professor Gregory C. Fu Thesis Supervisor Accepted by Professor Dietmar Seyferth Chai:.man, Departmental Committee on Graduate Students Science MASSACHISETTSINSTITUTE OF T4tNOL0(oy JUN 12 1995 This thesis has been examined by a committee of the Department of Chemistry as follows: Professor Gregory C. Fu _.- __ _ Thesis Supervisor Professor Frederick D. Greene - 2 THE DEVELOPMENT OF NEW ORGANOTIN REAGENTS FOR ORGANIC SYNTHESIS by Chee-Kiang Lim Submitted to the Department of Chemistry in partial fulfillment of the requirements for the Degree of Master of Science in Chemistry at the Massachusetts Institute of Technology ABSTRACT Organotin compounds have proved to be useful reagents for a wide range of reactions, but relatively few of these reactions have been made either catalytic or asymmetric. In this thesis, a new catalytic method for the formation of acylated cyanohydrins and the development of a new class of chiral stannacyclohexane catalysts are described. A convenient and efficient conversion of aldehydes to acylated cyanohydrins is catalyzed by tri-n-butyltin cyanide and pyruvonitrile. -
Cross-Electrophile Coupling of Unactivated Alkyl Chlorides † † Holt A
pubs.acs.org/JACS Communication Cross-Electrophile Coupling of Unactivated Alkyl Chlorides † † Holt A. Sakai, Wei Liu, Chi “Chip” Le, and David W. C. MacMillan* Cite This: J. Am. Chem. Soc. 2020, 142, 11691−11697 Read Online ACCESS Metrics & More Article Recommendations *sı Supporting Information ABSTRACT: Alkyl chlorides are bench-stable chemical feedstocks that remain among the most underutilized electrophile classes in transition metal catalysis. Overcoming intrinsic limitations of C(sp3)−Cl bond activation, we report the development of a novel organosilane reagent that can participate in chlorine atom abstraction under mild photocatalytic conditions. In particular, we describe the application of this mechanism to a dual nickel/photoredox catalytic protocol that enables the first cross-electrophile coupling of unactivated alkyl chlorides and aryl chlorides. Employing these low-toxicity, abundant, and commercially available organochloride building blocks, this methodology allows access to a broad array of highly functionalized C(sp2)−C(sp3) coupled adducts, including numerous drug analogues. ickel-catalyzed cross-electrophile coupling has become a their implementation in nickel-catalyzed cross-electrophile N well-accepted and powerful strategy for the rapid couplings.18 Within the realm of metal reductant-mediated assembly of C(sp3)-rich drug-like molecules, permitting nickel catalysis, strong C(sp3)−Cl bonds prevent the necessary convergent access to novel chemical space while introducing oxidative addition steps, while the accompanying