DOCSLIB.ORG

Tuning the Reactivity of Alkoxyl Radicals from 1,5-Hydrogen Atom Transfer To

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Tuning the Reactivity of Alkoxyl Radicals from 1,5-Hydrogen Atom Transfer To ARTICLE https://doi.org/10.1038/s41467-021-22382-y OPEN Tuning the reactivity of alkoxyl radicals from 1,5- hydrogen atom transfer to 1,2-silyl transfer Zhaoliang Yang1,4, Yunhong Niu1,4, Xiaoqian He2, Suo Chen1, Shanshan Liu 1, Zhengyu Li1, Xiang Chen1, ✉ ✉ Yunxiao Zhang1, Yu Lan 2,3 & Xiao Shen 1 Controlling the reactivity of reactive intermediates is essential to achieve selective trans- formations. Due to the facile 1,5-hydrogen atom transfer (HAT), alkoxyl radicals have been 1234567890():,; proven to be important synthetic intermediates for the δ-functionalization of alcohols. Herein, we disclose a strategy to inhibit 1,5-HAT by introducing a silyl group into the α-position of alkoxyl radicals. The efficient radical 1,2-silyl transfer (SiT) allows us to make various α- functionalized products from alcohol substrates. Compared with the direct generation of α- carbon radicals from oxidation of α-C-H bond of alcohols, the 1,2-SiT strategy distinguishes itself by the generation of alkoxyl radicals, the tolerance of many functional groups, such as intramolecular hydroxyl groups and C-H bonds next to oxygen atoms, and the use of silyl alcohols as limiting reagents. 1 The Institute for Advanced Studies, Engineering Research Center of Organosilicon Compounds and Materials, Ministry of Education, Wuhan University, Wuhan, People’s Republic of China. 2 School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing, People’s Republic of China. 3 College of Chemistry and Molecular Engineering, Zhengzhou University, ✉ Zhengzhou, People’s Republic of China. 4These authors contributed equally: Zhaoliang Yang, Yunhong Niu. email: [email protected];[email protected] NATURE COMMUNICATIONS | (2021) 12:2131 | https://doi.org/10.1038/s41467-021-22382-y | www.nature.com/naturecommunications 1 ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-021-22382-y adicals, anions, cations, carbenes, and others are key reac- and the tolerance of various C–H bonds and benzyl alcohols tive intermediates in synthesis1. These intermediates demonstrate the synthetic potential of our methodology R 30,31 usually show different reactivity, facilitating the develop- (Fig. 1c) . ment of complementary methodologies for the synthesis of molecules that are important in material and/or life-related Results field2–4. Among various radicals, alkoxyl radicals have gained – Radical 1,2-SiT in the synthesis of α-hydroxyl oxime ethers. increasing attention (Fig. 1a)5 9. Although the previous studies to Oximes and oxime ethers are important synthetic building blocks, generate alkoxyl radicals usually need pre-activated alcohols or – and they have also been found to be core structural motifs of corresponding precursors10 21, recent work on the direct activa- multiple bioactive molecules28,39–41. In 2018, Jiao and co-workers tion of alcohols with photocatalysis and/or transition-metal cat- – reported the synthesis of δ-alkoxylimino alcohols through 1,5- alysis largely broaden their synthetic utility22 29. When δ-C–H HAT of alkoxyl radicals, but no α-alkoxylimino alcohols were bonds are present, the intramolecular 1,5-hydrogen atom transfer isolated28. Previous methods to prepare α-hydroxyl oxime ethers (HAT) from the δ-position via a low-energy six-membered ring mainly rely on the reduction of alkoxyliminyl substituted ketones, transition state is usually favored over the transfer of hydrogen which themselves need multistep synthesis41. To the best of our atoms at other positions, thus alkoxyl radical-mediated δ-C–H knowledge, there is no report on radical-mediated synthesis of α- functionalization is widely studied (Fig. 1b)6. For example, the alkoxylimino alcohols. Therefore, we choose to investigate the synthesis of δ-alkoxylimino alcohols and intermolecular δ- reaction between α-silyl alcohol 1a and sulfonyl oxime ether 2 to heteroarylation of alcohols through 1,5-HAT of alkoxyl radicals – check whether α-functionalization product or δ-functionalization have been achieved (Fig. 1b)27 29. However, alkoxyl radical- product can be obtained. mediated α-functionalization of alcohols have not been reported30,31. It is also known that excess amount of alcohols are usually required in oxidative C–H functionalization reactions, Optimization of the reaction conditions for the synthesis of α- and it is challenging to control the selectivity when multiple hydroxyl oxime ethers. Previously, we found the Mn(II)/Mn oxidizable C–H bonds are present in the substrate30,31. Silicon (III)-catalyzed metal alkoxide (M-OR) homo-cleavage strategy possesses empty d orbitals and C–Si bond is longer than C–H was an efficient way to generate alkoxyl radicals for the direct bond. We envisioned that 1,2-silyl transfer (SiT) of alkoxyl radical transfer of trifluoroethanol and difluoroethanol units38. There- via three-membered ring transition state (also known as radical fore, we focused on the investigation of various transition-metal Brook rearrangement, RBR) might be easier than the corre- salts for M-OR homo-cleavage. After extensive investigations, we sponding 1,2-HAT and might be favored over 1,5-HAT process found that AgNO3 was a better pre-catalyst than CuCl2, FeCl3, – (Fig. 1c). NiBr2, Mn(OAc)3, and AgI (Fig. 2, entries 1 6). When the = RBR was initially proposed to explain the cyclopropanation reaction was carried out in MeCN/H2O (v/v 1:1) at 80 °C for product of the photoreaction between acylsilanes and electron- 12 h with K S O as an oxidant, a yield of 47% was afforded for – 2 2 8 poor olefins in 198132 35. However, the synthetic application of compound 3a, without any detection of δ-functionalization pro- 35–38 RBR was nearly ignored in the following decades . Until 2017, duct (entry 6). When the solvent was changed to acetone/H2O (v/ Smith and group found that benzylic radicals can be generated v = 1:1), the yield of α-functionalization product 3a increased to from the oxidation of hypervalent silicate intermediate by a 51% (entry 7). Increasing the concentration of the reaction photo-excited Ir complex37. In 2020, our group revealed that the resulted in an improved yield of compound 3a (71%, entry 8). – Mn-catalyzed RBR is superior to anion Brook rearrangement in Other oxidants such as Na2S2O8, (NH4)2S2O8, Dess Martin the direct trifluoroethanol transfer reactions38. Herein, we show periodinane, and tert-butyl peroxybenzoate afforded lower effi- that radical 1,2-SiT is favored over 1,5-HAT under Ag-catalysis ciency of the reaction (entries 9–12). Lowering the reaction conditions, and selective α-C–C bond formation reactions are temperature also resulted in a decreased yield of compound 3a achieved without any δ-functionalization product, in which the (entries 13 and 14). The control experiment showed that, without use of alcohols as limiting reagents in the reaction of oxime ethers AgNO3, only 20% yield of compound 3a was observed by proton a Alkoxyl radicals: important synthetic intermediates c This work: 1,2-SiT of alkoxyl radicals which contain d-C-H bonds O disfavored OH OH R' R' 1,2-SiT H H Ag O O[Si] R'' [Si] R H R H R favored R R' R' [Si] b Previous work: selective 1,5-HAT of alkoxyl radicals [Si]: silyl group OH favored R' R' 1,5-HAT OH H OH R'' H O R examples of products: R H H H R R' disfavored R H R' H OH OH OH O CN O NOBn OH OH Cl Ar H H H NOBn representative no products derived H H N NC H X H from 1,2-HAT R examples: R' R R' reactive C-H bonds in 1,5-HAT H : ref 28 ref 27, 29 and oxidative C-H functionalizations Fig. 1 Tuning the reactivity of alkoxyl radicals from 1,5-HAT to 1,2-SiT by the incorporation of a silyl group. a Alkoxyl radicals are important synthetic intermediates. b Intramolecular 1,5-hydrogen atom transfer (HAT) via a six-membered ring transition state is usually favored over the transfer of hydrogen atoms at other positions, thus alkoxyl radicals mediated δ-C–H functionalization is widely studied. c We disclose here that 1,2-silyl transfer (SiT) is favored over 1,5-HAT under Ag-catalyzed conditions, allowing the efficient synthesis of α-hydroxyl oxime ethers and α-heteroaryl alcohols (this work). The alkoxyl radical-mediated reactions can tolerate many reactive C–H bonds, which are reactive in 1,5-HAT and oxidative C–H functionalizations. Another OH group in the substrates can also be tolerated. 2 NATURE COMMUNICATIONS | (2021) 12:2131 | https://doi.org/10.1038/s41467-021-22382-y | www.nature.com/naturecommunications NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-021-22382-y ARTICLE Fig. 2 Reaction optimization. aThe mixture of 1a (0.2 mmol), catalyst (0.04 mmol), oxidant (0.4 mmol), and 2 (0.3 mmol) in the solvent (2 mL) was 1 b stirred at T under N2 for 12 h. Conversions of 1a and 2 and yield of 3a were determined by H NMR using BrCH2CH2Br as an internal standard. Solvent (1.5 mL). DMP Dess–Martin periodinane, TBPB tert-butyl peroxybenzoate. AgNO3 (20 mol%) NOBn [Si] NOBn K2S2O8 ( 2 equiv.) + CN OH PhO S CN n-C H H 2 Acetone/H O (1:1) OH 3 7 2 n o -C3H7 H 1 2 (1.5 equiv.) 80 C, 12 h 3a 1) with 1a ([Si] = PhMe2 Si), >99 conv. of 1a, 86% conv. of 2, 71% yield of 3a; 2) with 1ab ([Si] = Me3 Si), >99 conv. of 1ab, 91% conv. of 2, 41% yield of 3a; 3) with 1ac([Si] = t-BuMe2Si), >99 conv. of 1ac, 92% conv. of 2, 13% yield of 3a; 4) with 1ad ([Si] = Ph2MeSi), 92% conv.of 1ad,90% conv.
Load more

Recommended publications
  • Electronic Structures and Spin Topologies of #-Picoliniumyl Radicals
    Subscriber access provided by UNIV OF MISSOURI COLUMBIA Article Electronic Structures and Spin Topologies of #-Picoliniumyl Radicals. A Study of the Homolysis of N-Methyl-#-picolinium and of Benzo-, Dibenzo-, and Naphthoannulated Analogs Rainer Glaser, Yongqiang Sui, Ujjal Sarkar, and Kent S. Gates J. Phys. Chem. A, 2008, 112 (21), 4800-4814 • DOI: 10.1021/jp8011987 • Publication Date (Web): 22 May 2008 Downloaded from http://pubs.acs.org on December 12, 2008 More About This Article Additional resources and features associated with this article are available within the HTML version: • Supporting Information • Access to high resolution figures • Links to articles and content related to this article • Copyright permission to reproduce figures and/or text from this article The Journal of Physical Chemistry A is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 4800 J. Phys. Chem. A 2008, 112, 4800–4814 Electronic Structures and Spin Topologies of γ-Picoliniumyl Radicals. A Study of the Homolysis of N-Methyl-γ-picolinium and of Benzo-, Dibenzo-, and Naphthoannulated Analogs Rainer Glaser,*,† Yongqiang Sui,† Ujjal Sarkar,† and Kent S. Gates*,†,‡ Departments of Chemistry and Biochemistry, UniVersity of Missouri-Columbia, Columbia, Missouri 65211 ReceiVed: February 9, 2008 Radicals resulting from one-electron reduction of (N-methylpyridinium-4-yl) methyl esters have been reported to yield (N-methylpyridinium-4-yl) methyl radical, or N-methyl-γ-picoliniumyl for short, by heterolytic cleavage of carboxylate. This new reaction could provide the foundation for a new structural class of bioreductively activated, hypoxia-selective antitumor agents. N-methyl-γ-picoliniumyl radicals are likely to damage DNA by way of H-abstraction and it is of paramount significance to assess their H-abstraction capabilities.
    [Show full text]
  • Electron Ionization
    Chapter 6 Chapter 6 Electron Ionization I. Introduction ......................................................................................................317 II. Ionization Process............................................................................................317 III. Strategy for Data Interpretation......................................................................321 1. Assumptions 2. The Ionization Process IV. Types of Fragmentation Pathways.................................................................328 1. Sigma-Bond Cleavage 2. Homolytic or Radical-Site-Driven Cleavage 3. Heterolytic or Charge-Site-Driven Cleavage 4. Rearrangements A. Hydrogen-Shift Rearrangements B. Hydride-Shift Rearrangements V. Representative Fragmentations (Spectra) of Classes of Compounds.......... 344 1. Hydrocarbons A. Saturated Hydrocarbons 1) Straight-Chain Hydrocarbons 2) Branched Hydrocarbons 3) Cyclic Hydrocarbons B. Unsaturated C. Aromatic 2. Alkyl Halides 3. Oxygen-Containing Compounds A. Aliphatic Alcohols B. Aliphatic Ethers C. Aromatic Alcohols D. Cyclic Ethers E. Ketones and Aldehydes F. Aliphatic Acids and Esters G. Aromatic Acids and Esters 4. Nitrogen-Containing Compounds A. Aliphatic Amines B. Aromatic Compounds Containing Atoms of Nitrogen C. Heterocyclic Nitrogen-Containing Compounds D. Nitro Compounds E. Concluding Remarks on the Mass Spectra of Nitrogen-Containing Compounds 5. Multiple Heteroatoms or Heteroatoms and a Double Bond 6. Trimethylsilyl Derivative 7. Determining the Location of Double Bonds VI. Library
    [Show full text]
  • Mechanistic Approach to Thermal Production of New Materials from Asphaltenes of Castilla Crude Oil
    processes Article Mechanistic Approach to Thermal Production of New Materials from Asphaltenes of Castilla Crude Oil Natalia Afanasjeva 1, Andrea González-Córdoba 2,* and Manuel Palencia 1 1 Department of Chemistry, Faculty of Natural and Exact Science, Universidad del Valle, Cali 760020, Colombia; [email protected] (N.A.); [email protected] (M.P.) 2 Department of Chemical and Environmental Engineering, Faculty of Engineering, Universidad Nacional de Colombia, Bogotá 111321, Colombia * Correspondence: [email protected]; Tel.: +57-1-316-5000 (ext. 14322) Received: 16 August 2020; Accepted: 23 October 2020; Published: 12 December 2020 Abstract: Asphaltenes are compounds present in crude oils that influence their rheology, raising problems related to the extraction, transport, and refining. This work centered on the chemical and structural changes of the asphaltenes from the heavy Colombian Castilla crude oil during pyrolysis between 330 and 450 ◦C. Also, the development of new strategies to apply these macromolecules, and the possible use of the cracking products as a source of new materials were analyzed. The obtained products (coke, liquid, and gas) were collected and evaluated through the techniques of proton and carbon-13 nuclear magnetic resonance (1H and 13C NMR), elemental composition, Fourier-transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), saturates, aromatics, resins, and asphaltenes (SARA) analysis, and gas chromatography–mass spectrometry (GC-MS). A comparison of the applied methods showed that the asphaltene molecules increased the average size of their aromatic sheets, lost their aliphatic chains, condensed their aromatic groups, and increased their degree of unsaturation during pyrolysis. In the liquid products were identified alkylbenzenes, n-alkanes C9–C30, and n-alkenes.
    [Show full text]
  • Hydrogen Peroxide As a Hydride Donor and Reductant Under Biologically Relevant Conditions† Cite This: Chem
    Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue Hydrogen peroxide as a hydride donor and reductant under biologically relevant conditions† Cite this: Chem. Sci.,2019,10,2025 ab d c All publication charges for this article Yamin Htet, Zhuomin Lu, Sunia A. Trauger have been paid for by the Royal Society and Andrew G. Tennyson *def of Chemistry Some ruthenium–hydride complexes react with O2 to yield H2O2, therefore the principle of microscopic À reversibility dictates that the reverse reaction is also possible, that H2O2 could transfer an H to a Ru complex. Mechanistic evidence is presented, using the Ru-catalyzed ABTScÀ reduction reaction as a probe, which suggests that a Ru–H intermediate is formed via deinsertion of O2 from H2O2 following Received 5th December 2018 À coordination to Ru. This demonstration that H O can function as an H donor and reductant under Accepted 7th December 2018 2 2 biologically-relevant conditions provides the proof-of-concept that H2O2 may function as a reductant in DOI: 10.1039/c8sc05418e living systems, ranging from metalloenzyme-catalyzed reactions to cellular redox homeostasis, and that À rsc.li/chemical-science H2O2 may be viable as an environmentally-friendly reductant and H source in green catalysis. Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Introduction bond and be subsequently released as H2O2 (Scheme 1A, red arrows).12,13 The principle of microscopic reversibility14 there- Hydrogen peroxide and its descendant reactive oxygen species fore dictates that it is mechanistically equivalent for H2O2 to (ROS) have historically been viewed in biological systems nearly react with a Ru complex and be subsequently released as O2 exclusively as oxidants that damage essential biomolecules,1–3 with concomitant formation of a Ru–H intermediate (Scheme but recent reports have shown that H2O2 can also perform 1A, blue arrows).
    [Show full text]
  • Structure, Stability, and Substituent Effects in Aromatic S-Nitrosothiols: the Crucial Effect of a Cascading Negative Hyperconjugation/Conjugation Interaction
    Marquette University e-Publications@Marquette Chemistry Faculty Research and Publications Chemistry, Department of 10-23-2014 Structure, Stability, and Substituent Effects in Aromatic S-Nitrosothiols: The Crucial Effect of a Cascading Negative Hyperconjugation/Conjugation Interaction Matthew Flister Marquette University, [email protected] Qadir K. Timerghazin Marquette University, [email protected] Follow this and additional works at: https://epublications.marquette.edu/chem_fac Part of the Chemistry Commons Recommended Citation Flister, Matthew and Timerghazin, Qadir K., "Structure, Stability, and Substituent Effects in Aromatic S-Nitrosothiols: The Crucial Effect of a Cascading Negative Hyperconjugation/Conjugation Interaction" (2014). Chemistry Faculty Research and Publications. 360. https://epublications.marquette.edu/chem_fac/360 Marquette University e-Publications@Marquette Chemistry Faculty Research and Publications/College of Arts and Sciences This paper is NOT THE PUBLISHED VERSION; but the author’s final, peer-reviewed manuscript. The published version may be accessed by following the link in the citation below. Journal of Physical Chemistry : A, Vol. 18, No. 42 (October 23, 2014): 9914–9924. DOI. This article is © American Chemical Society Publications and permission has been granted for this version to appear in e-Publications@Marquette. American Chemical Society Publications does not grant permission for this article to be further copied/distributed or hosted elsewhere without the express permission from American Chemical Society Publications. Structure, Stability, and Substituent Effects in Aromatic S-Nitrosothiols: The Crucial Effect of a Cascading Negative Hyperconjugation/Conjugation Interaction Matthew Flister Department of Chemistry, Marquette University, Milwaukee, Wisconsin Qadir K. Timerghazin Department of Chemistry, Marquette University, Milwaukee, Wisconsin Abstract Aromatic S-nitrosothiols (RSNOs) are of significant interest as potential donors of nitric oxide and related biologically active molecules.
    [Show full text]
  • Development of a High-Density Initiation Mechanism for Supercritical Nitromethane Decomposition
    The Pennsylvania State University The Graduate School DEVELOPMENT OF A HIGH-DENSITY INITIATION MECHANISM FOR SUPERCRITICAL NITROMETHANE DECOMPOSITION A Thesis in Mechanical Engineering by Christopher N. Burke © 2020 Christopher N. Burke Submitted in Partial Fulfillment of the Requirements for the Degree of Master of Science August 2020 The thesis of Christopher N. Burke was reviewed and approved by the following: Richard A. Yetter Professor of Mechanical Engineering Thesis Co-Advisor Adrianus C. van Duin Professor of Mechanical Engineering Thesis Co-Advisor Jacqueline A. O’Connor Professor of Mechanical Engineering Karen Thole Professor of Mechanical Engineering Mechanical Engineering Department Head ii Abstract: This thesis outlines the bottom-up development of a high pressure, high- density initiation mechanism for nitromethane decomposition. Using reactive molecular dynamics (ReaxFF), a hydrogen-abstraction initiation mechanism for nitromethane decomposition that occurs at initial supercritical densities of 0.83 grams per cubic centimeter was investigated and a mechanism was constructed as an addendum for existing mechanisms. The reactions in this mechanism were examined and the pathways leading from the new initiation set into existing mechanism are discussed, with ab-initio/DFT level data to support them, as well as a survey of other combustion mechanisms containing analogous reactions. C2 carbon chemistry and soot formation pathways were also included to develop a complete high-pressure mechanism to compare to the experimental results of Derk. C2 chemistry, soot chemistry, and the hydrogen-abstraction initiation mechanism were appended to the baseline mechanism used by Boyer and analyzed in Chemkin as a temporal, ideal gas decomposition. The analysis of these results includes a comprehensive discussion of the observed chemistry and the implications thereof.
    [Show full text]
  • Understanding Metal-Metal Bonds in Heterobimetallic Complexes and Their Use As Catalysts for Dinitrogen Conversion
    Understanding Metal-Metal Bonds in Heterobimetallic Complexes and Their Use as Catalysts for Dinitrogen Conversion A DISSERTATION SUBMITTED TO THE FACULTY OF THE UNIVERSITY OF MINNESOTA BY Laura J. Clouston IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY Connie C. Lu, Advisor July 2016 © Laura J Clouston 2016 Acknowledgments I am grateful to obtain my degree from the Chemistry Department at the University of Minnesota, were I could not be surrounded by better people. I was lucky to be a part of the Lu group, where I could always find someone to talk science or have a good laugh. I would like to thank Connie for welcoming me into the group and providing me with numerous opportunities to grow as a scientist. Thanks to the rest of the Lu group, past and present, you have all taught me something valuable that I will keep with me. Thanks to Deanna for guiding me through my first two years, and to Steve, Reed and Ryan for always keeping my expectations high. Thanks to Dave, the second year crew- Matt, Bianca, JT and Sai, and Azim for keeping the lab to be a fun place to spend the majority of your time. A special thanks to the Gagliardi group for a great collaboration, especially Varinia, who has calculated almost everything I have made or wanted to make, I have truly enjoyed working together. I am also thankful for the groups in the department that I have worked closely with, the Tonks, Tolman, Que, Ellis and Hoye groups, who have provided a wealth of advice, resources and chemicals throughout my graduate work.
    [Show full text]
  • View of Bicyclic Cobalt Cation 42
    University of Alberta Cobalt(III)-Mediated Cycloalkenyl-Alkyne Cycloaddition and Cycloexpansion Reactions by Bryan Chi Kit Chan A thesis submitted to the Faculty of Graduate Studies and Research in partial fulfillment of the requirements for the degree of Doctor of Philosophy Chemistry ©Bryan Chi Kit Chan Spring 2010 Edmonton, Alberta Permission is hereby granted to the University of Alberta Libraries to reproduce single copies of this thesis and to lend or sell such copies for private, scholarly or scientific research purposes only. Where the thesis is converted to, or otherwise made available in digital form, the University of Alberta will advise potential users of the thesis of these terms. The author reserves all other publication and other rights in association with the copyright in the thesis and, except as herein before provided, neither the thesis nor any substantial portion thereof may be printed or otherwise reproduced in any material form whatsoever without the author's prior written permission. Examining Committee Jeffrey M. Stryker, Chemistry, University of Alberta Martin Cowie, Chemistry, University of Alberta Jillian M. Buriak, Chemistry, University of Alberta Frederick G. West, Chemistry, University of Alberta William C. McCaffrey, Chemical Engineering, University of Alberta Lisa Rosenberg, Chemistry, University of Victoria Abstract A comprehensive investigation of cycloalkenyl-alkyne coupling reactions mediated by cobalt(III) templates is presented. The in situ derived cationic η3- cyclohexenyl complexes of cobalt(III) react with some terminal alkynes to afford either η1,η4-bicyclo[4.3.1]decadienyl or η2,η3-vinylcyclohexenyl products, depending on the type and concentration of the alkyne. The mechanism for this cyclohexenyl-alkyne cycloaddition reaction is consistent with the previously reported cobalt-mediated [3 + 2 + 2] allyl-alkyne coupling reaction.
    [Show full text]
  • Streamlining Free Radical Green Chemistry
    Streamlining Free Radical Green Chemistry V. Tamara Perchyonok VTPCHEM PTY LTD, Melbourne, Victoria, Australia Ioannis Lykakis Department of Chemistry, University of Crete, Voutes-Heraklion, Greece AI Postigo Faculty of Science, University of Belgrano, Buenos Aires, Argentina RSC Publishing Contents and Chapter 1 Development of Free Radical Green Chemistry Technology: Journey through Times, Solvents, Causes, Effects and Assessments 1.1 Introduction 1 1.2 The Major Use of Free Radical Green Chemistry from the Beginning 4 4 1.3 Alternative Feedstocks 5 1.3.1 Innocuous or More Innocuous 1.3.2 Renewable 5 1.3.3 Light 5 1.3.4 Solve Other Environmental Problems 6 1.3.5 Biocatalysis 6 7 1.4 Benign Reagents/Synthetic Pathways 7 1.4.1 Innocuous or More Innocuous 1.4.2 Generates Less Waste 7 1.4.3 Selective 8 1.4.4 Catalytic 8 8 1.5 Biomass: Utilization and Sustainability 9 1.6 Green Chemical Syntheses and Processes 1.7 Basic Radical Chemistry: Structure, Reactions and Rates 10 1.7.1 General Aspects of Synthesis with Radicals: Advantages and Traditions 10 1.7.2 Reactions Between Radicals 10 1.7.3 Reaction Between a Radical and a Non-radical 10 1.7.4 Reactivity and Selectivity 11 11 1.7.5 Enthalpy: In Brief 13 1.7.6 Entropy 1.7.7 Steric Effects 14 1.7.8 Stereoelectronic Effects 15 Streamlining Free Radical Green Chemistry V. Tamara Perchyonok, Ioannis Lykakis and Al Postigo 2012 © V. Tamara Perchyonok, Ioannis Lykakis and AI Postigo Published by the Royal Society of Chemistry, www.rsc.org ix X Contents 1.7.9 Polarity 17 1.8 Solvent Effect and Free
    [Show full text]
  • Improving the Accuracy of Density Functional Theory (DFT
    Int. J. Mol. Sci. 2011, 12, 2242-2261; doi:10.3390/ijms12042242 OPEN ACCESS International Journal of Molecular Sciences ISSN 1422-0067 www.mdpi.com/journal/ijms Article Improving the Accuracy of Density Functional Theory (DFT) Calculation for Homolysis Bond Dissociation Energies of Y-NO Bond: Generalized Regression Neural Network Based on Grey Relational Analysis and Principal Component Analysis Hong Zhi Li 1, Wei Tao 1, Ting Gao 2, Hui Li 2, Ying Hua Lu 1,2,* and Zhong Min Su 1,* 1 Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun, 130024, China; E-Mails: [email protected] (H.Z.L.); [email protected] (W.T.) 2 School of Computer Science and Information Technology, Northeast Normal University, Changchun, 130017, China; E-Mails: [email protected] (T.G.); [email protected] (H.L.) * Authors to whom correspondence should be addressed; E-Mail: [email protected] (Y.H.L.); [email protected] (Z.M.S.); Tel.: +86-0431-85099108; Fax: +86-431-85684009. Received: 2 February 2011; in revised form: 21 February 2011 / Accepted: 31 March 2011 / Published: 1 April 2011 Abstract: We propose a generalized regression neural network (GRNN) approach based on grey relational analysis (GRA) and principal component analysis (PCA) (GP-GRNN) to improve the accuracy of density functional theory (DFT) calculation for homolysis bond dissociation energies (BDE) of Y-NO bond. As a demonstration, this combined quantum chemistry calculation with the GP-GRNN approach has been applied to evaluate the homolysis BDE of 92 Y-NO organic molecules. The results show that the full-descriptor GRNN without GRA and PCA (F-GRNN) and with GRA (G-GRNN) approaches reduce the root-mean-square (RMS) of the calculated homolysis BDE of 92 organic molecules from 5.31 to 0.49 and 0.39 kcal mol−1 for the B3LYP/6-31G (d) calculation.
    [Show full text]
  • LA.2.1 Reaction Mechanisms
    LA.2.1 Reaction Mechanisms Curly Arrows In a chemical reaction bonds are broken and new bonds made. A reaction mechanism describes the steps involved and makes it clear how these bonds are formed and broken. The slowest step in the reaction is known as the RATE DETERMINING STEP. Curly arrows represent the movement of electrons. A FULL arrow represents an electron pair (see Figure 1) whereas a HALF arrow represents a single electron (see Figure 2) which is traditionally reserved for radical chemistry. H+ + Cl- 2Cl Figure 1 The heterolysis of HCl Figure 2 The homolysis of Cl2 When a bond is broken and both electrons go to the same atom (represented by a full arrow), this is called HETEROLYTIC FISSION. When a bond is broken and the bonding electrons are evenly split (represented by a half arrow), this is called HOMOLYTIC FISSION. Nucleophiles Electrophiles Definition: Electron pair DONOR. Nucleophiles Definition: Electron pair ACCEPTOR. are also known as Lewis bases. Electrophiles are also known as Lewis acids. Compounds which act as nucleophiles have a Compounds which act as electrophiles are high electron density electron deficient Common nucleophiles: Common electrophiles: - - - + + + Anions CN, OH, Cl Cations H , CH3 , NO2 Π Bonds Alkenes, Alkynes, Polar molecules Haloalkanes, Ketones, (electrophilic site at δ+) Aromatic compounds e.g benzene Alcohols Atoms with Lone Amines, Ketones, Pairs Electron movement always goes from the nucleophile to the electrophile: Water Electrophilic Addition to Alkenes (Bromination) A classic test for alkenes is the addition of bromine (Br2) as the presence of an alkene such as ethene, changes the brown bromine to colourless.
    [Show full text]
  • Organic Chemistry I
    Organic Chemistry I Mohammad Jafarzadeh Faculty of Chemistry, Razi University Organic Chemistry, Structure and Function (7th edition) By P. Vollhardt and N. Schore, Elsevier, 2014 1 98 CHAPTER 3 Reactions of Alkanes 3-1 STRENGTH OF ALKANE BONDS: RADICALS 98 CHAPTER 3 Reactions of Alkanes In Section 1-2 we explained how bonds are formed and that energy is released on bond formation. For example, bringing two hydrogen atoms into bonding distance produces 104 kcal mol21 (435 kJ mol21) of heat (refer to Figures 1-1 and 1-12). 3-1 STRENGTH OF ALKANE BONDS: RADICALS Bond making 21 21 In Section 1-2 we explained how bonds are formed and that energy is released on bond H? 1 H? uuuuy HOH DH 8 5 2104 kcal mol (2435 kJ mol ) formation. For example, bringing two hydrogen atoms into bonding distance produces Released heat: exothermic 104 kcal mol21 (435 kJ mol21) of heat (refer to Figures 1-1 and 1-12). Bond making Consequently, breaking such a bond requires heat—in fact, the same amount of heat that uuuuy 21 21 H? 1 H? HOH DH 8 5 2104 kcal mol (2435 kJ mol ) was released when the bond was made. This energy is called bond-dissociation energy, DH8, Released heat: exothermic 3. Reaction of Alkanes and is a quantitative measure of the bond strength. Consequently, breakingHomolytic suchCleavage a bond requires: Bonding heat—inElectrons fact, theSeparate same amount of heat that was released when the bond was made. This energy is called bond-dissociation energy, DH8, Bond breaking and is a quantitativeThe bondmeasureBreaks of thein bondsuch strength.a way that the two bonding electrons divide equally between the HOH uuuuy H? 1 H? DH 8 5 DH 8 5 104 kcal mol21 (435 kJ mol21) two participating atoms or fragments.
    [Show full text]