Applications of Radical Reactions for the Synthesis of -Amino Acids and Carbonyl Compounds

Total Page:16

File Type:pdf, Size:1020Kb

Applications of Radical Reactions for the Synthesis of -Amino Acids and Carbonyl Compounds Applications of radical reactions for the synthesis of β-amino acids and carbonyl compounds Xuan Chen To cite this version: Xuan Chen. Applications of radical reactions for the synthesis of β-amino acids and carbonyl com- pounds. Organic chemistry. Institut Polytechnique de Paris, 2020. English. NNT : 2020IPPAX042. tel-02983194 HAL Id: tel-02983194 https://tel.archives-ouvertes.fr/tel-02983194 Submitted on 29 Oct 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Applications of radical reactions for the synthesis of β-amino acids and carbonyl compounds 42 0 Thèse de doctorat de l’Institut Polytechnique de Paris AX préparée à École Polytechnique IPP 20 20 École doctorale n°626 Ecole Doctorale de l’Institut Polytechnique de : Paris (ED IP Paris) Spécialité de doctorat: Chimie NNT Thèse présentée et soutenue à Palaiseau, le 15 Septembre 2020, par M. Xuan CHEN Composition du Jury : Isabelle GILLAIZEAU Professeur, Université d'Orléans (UMR 7311) Présidente Luc NEUVILLE Docteur, University Paris-Saclay Rapporteur Benoît CROUSSE Docteur, University Paris-Sud (UMR 8076) Rapporteur Samir Z. ZARD Professeur, Ecole Polytechnique (UMR 7652) Examinateur, Directeur de thèse Acknowledgements I First of all, I am going to express my gratitude to my supervisor Professor Samir Z. Zard who gave me an opportunity to learn in a top university of the world and guided me on the right pathway in my academic career. I still remember the first day that I went to his office, he taught me the basic principle of xanthate chemistry and outlined the research topics in the next three years with profound knowledge. From that time, I changed my view on radical chemistry and realized xanthate transfer process is a powerful tool in organic synthesis. He not only gave me many helps in my research and daily life but also taught me the philosophy of life, the word “you should happy for your success, but more importantly, you should learn from your failure” impressed me the most. I really appreciate everything that he did for me and it is a great honor to work as his Ph.D student. I would like to thank all the members of jury committee, Prof. Isabelle Gillaizeau, Dr. Luc Neuville and Dr. Benoît Crousse for your precious time to evaluate this manuscript and come to my defense. Thank you for your suggestions. I want to thank Dr. Alexis Archambeau and Dr. Sébastien Prévost who have made great efforts on the problem sessions part, it is helpful to me and push me forward, I learned a lot from these exercises during the three years. My special thanks to Dr. Qi HUANG, a former Ph.D student in LSO. He gave me countless help at the beginning of my abroad life, both in my research projects and some trivial personal things and taking time to read and correct this manuscript. The two years we shared is unforgettable in my life. I also want to thank Vincent R. and Richard L. for providing me many solutions to the problem I encountered in my experiments and gave me some practical tips in my research projects. And also thank them for reading and correction of this manuscript. I would like to thank all of the LSO members: Dr. Yvan, Dr. Bastien Nay, Antoine, Anaïs, Wei, Oscar, Quentin, Gabriela, Dung, Xianzhu, Jean, Benjamin, Valentin, Nicolas, Paula, Cristina, Thomas, Kieu, Eloi, Pjotr. And also express my grateful to Julien for his warm help in many administrative matters and Vincent L. for HRMS analysis. I would like to thank my family, relatives and friends, they always stand behind me and help me to achieve the goals. I express my deepest gratitude to my parents and my wife for their support. Finally, I especially want to thank my little daughter, her cute face and sweet smile give me the courage and confidence to overcome any difficulties I encountered, and bring me a joyful life. Thank you all! II Contents III Acknowledgements ................................................................................................................... I Abbreviations ....................................................................................................................... VII Avant-Propos .......................................................................................................................... IX General introduction ........................................................................................................... XII Chapter 1 Introduction to radical chemistry ........................................................................ 1 1.1 Introduction .................................................................................................................... 2 1.2 Physical properties of radicals ....................................................................................... 2 1.2.1 The geometry: planar or pyramidal? ..................................................................... 2 1.2.2 Radical stability .................................................................................................... 3 1.3 Chemical properties of radicals ..................................................................................... 5 1.3.1 Thermal cleavage .................................................................................................. 5 1.3.2 Photochemical cleavage ........................................................................................ 6 1.3.3 Radicals arising from organoboranes .................................................................... 7 1.3.4 Radicals generated by single electron transfer process (SET) .............................. 8 1.4 Radical reactions ............................................................................................................ 8 1.4.1 Radical chain reactions ......................................................................................... 8 1.4.2 Hydrogen abstraction ............................................................................................ 9 1.4.3 Addition to unsaturated bonds ............................................................................ 10 1.4.4 Fragmentation ..................................................................................................... 10 1.4.5 Rearrangement ..................................................................................................... 11 1.4.6 Radical Oxidation ................................................................................................ 11 1.5 Conclusion ................................................................................................................... 12 Chapter 2 Xanthate based radical chemistry ...................................................................... 15 2.1 Introduction .................................................................................................................. 16 2.2 The Barton-McCombie deoxygenation ........................................................................ 16 2.2.1 An overall view: from alcohol to alkane ............................................................. 16 IV 2.2.2 The mechanism ................................................................................................... 17 2.2.3 Applications ........................................................................................................ 17 2.3 Development of the Barton-McCombie deoxygenation .............................................. 18 2.4 Radicals generation from carbon-sulfur bond disconnection: the degenerate transfer of xanthates .............................................................................................................................. 20 2.5 Preparation of xanthates ............................................................................................... 22 2.5.1 By a simple substitution ...................................................................................... 22 2.5.2 Using a radical procedure ................................................................................... 23 2.5.3 Other radical approaches ..................................................................................... 24 2.6 Applications of xanthate chemistry .............................................................................. 25 2.6.1 Applications of radical additions to the synthesis of ketones ............................. 25 2.6.2 Formation of cyclopropanes ............................................................................... 27 2.6.3 The xanthate route to amines and anilines .......................................................... 28 2.6.4 Stabilization of Radicals by Imides. ................................................................... 30 2.6.5 Synthesis of protected amino acid derivatives .................................................... 31 2.6.6 Modification of heterocycles .............................................................................. 32 2.7 Conclusion ................................................................................................................... 36 Chapter 3 A Convergent Route to β-Amino Acids and
Recommended publications
  • Chemistry Department 32.Pdf (10.36Mb)
    THE FABRICATION OF NANOMETRIC METAL SULFIDES FROM XANTHATE PRECURSORS By ALAN PIQUETTE Bachelor of Arts Western State College of Colorado Gunnison, Colorado 2002 Submitted to the Faculty of the Graduate College of the Oklahoma State University In partial fulfillment of The requirements for The Degree of DOCTOR OF PHILOSOPHY December, 2007 THE FABRICATION OF NANOMETRIC METAL SULFIDES FROM XANTHATE PRECURSORS Thesis Approved: _______________ __Allen Apblett___ ______________ Thesis Advisor ________________ Nicholas Materer_____ __________ _____________ __LeGrande Slaughter___ __________ _______________ ____Jim Smay___ _______________ _____________ __A. Gordon Emslie___ ____________ Dean of the Graduate College ACKNOWLEDGEMENTS It is with my utmost sincere appreciation that I acknowledge my thesis advisor, Dr. Allen W. Apblett, for his support, guidance, and motivation. He provided a research environment that was both friendly and challenging, which made my years in his group enjoyable and rewarding. His broad range of knowledge was something of which I was happy to take advantage. His dedication to teaching and research is something that will be a positive influence on me for the rest of my scientific career. I would like to express gratitude to my committee members: Dr. Nicholas Materer, Dr. LeGrande Slaughter, and Dr. Jim Smay, for their assistance, advice, guidance, and support throughout the years. I am deeply grateful to all my colleagues and friends in the chemistry department. I would specifically like to thank Sulaiman Al-Fadul, Mohammed Al-Hazmi, Zeid Al- Othmann, Mohamed Chehbouni, Satish Kuriyavar, and Tarek Trad for showing me the ropes, for their valuable discussions, continuous encouragement, and for all the help they extended during the course of my stay in the Apblett Group.
    [Show full text]
  • I the Synthesis of Papyracillic Acids: Application of the Tandem Chain
    University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Winter 2011 I The synthesis of papyracillic acids: Application of the tandem chain extension-acylation reaction II Diastereoselective synthesis of beta-methyl-gamma-keto esters through the utility of an L- serine auxiliary Jennifer R. Mazzone University of New Hampshire, Durham Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation Mazzone, Jennifer R., "I The synthesis of papyracillic acids: Application of the tandem chain extension- acylation reaction II Diastereoselective synthesis of beta-methyl-gamma-keto esters through the utility of an L-serine auxiliary" (2011). Doctoral Dissertations. 644. https://scholars.unh.edu/dissertation/644 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]. I. THE SYNTHESES OF PAPYRACILLIC ACIDS: APPLICATION OF THE TANDEM CHAIN EXTENSION-ACYLATION REACTION II. DIASTEREOSELECTIVE SYNTHESIS OF p-METHYL-y-KETO ESTERS THROUGH THE UTILITY OF AN L-SERINE AUXILIARY BY Jennifer R. Mazzone B.A., Assumption College, 2006 DISSERTATION Submitted to the University of New Hampshire in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Chemistry December, 2011 UMI Number: 3500790 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted.
    [Show full text]
  • Arenechromium Tricarbonyl Complexes: Conformational
    η6 – ARENECHROMIUM TRICARBONYL COMPLEXES: CONFORMATIONAL ANALYSIS, STEREOCONTROL IN NUCLEOPHILIC ADDITION AND APPLICATIONS IN ORGANIC SYNTHESIS by HARINANDINI PARAMAHAMSAN Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy Thesis Advisor: Prof. Anthony J. Pearson Department of Chemistry CASE WESTERN RESERVE UNIVERSITY May 2005 CASE WESTERN RESERVE UNIVERSITY SCHOOL OF GRADUATE STUDIES We hereby approve the dissertation of Harinandini Paramahamsan candidate for the Ph.D. degree*. (signed) Prof. Philip P. Garner (Chair of the Committee, Department of Chemistry, CWRU) Prof. Anthony J. Pearson (Department of Chemistry, CWRU) Prof. Fred L. Urbach (Department of Chemistry, CWRU) Dr. Zwong-Wu Guo (Department of Chemistry, CWRU) Dr. Stuart J. Rowan (Department of Macromolecular Science and Engineering, CWRU) Date: 14th January 2005 *We also certify that written approval has been obtained for any propriety material contained therein. To Amma, Naina & all my Teachers Table of Contents List of Tables………………………………………………………………………..……iv List of Figures…………………………………………………………………….…........vi List of Schemes…………………………………………………………………….….….ix List of Equations………………………………………………………...……….……….xi Acknowledgements………………………………………………………….…..……….xii List of Abbreviations……………………………………………………………………xiv Abstract………………………………………………………………………………….xvi CHAPTER I........................................................................................................................ 1 I.1 Structure and Bonding ...........................................................................................
    [Show full text]
  • Transcription 11.12.07
    Lab 17A • 12/07/11 [lab quiz] Nomenclature of alkenes The first molecule that I want to look at is this one, where we have the two methyl groups on one side, two hydrogens on the other side. Would it be appropriate to use cis or trans, or E or Z, or both, or neither? One carbon of the double bond versus the other, those are the two different sides of the double, then the top versus the bottom are the two faces of the double bond. If we notice, on both the top face and the bottom face, we have a methyl group that is pointed the same way as a hydrogen. There is a steric factor as far as what alkene would prefer to form thermodynamically, so there is an importance that there’s some interaction there. That methyl group with one hydrogen is exactly the same interaction as you’d have the methyl group and the other hydrogen pointed the opposite way – meaning that if you were to switch the two hydrogens, you’d end up with exactly the same molecule again. The only reason that we use the term cis or trans or E or Z is to describe that it is one configuration versus another, but since there’s only one configuration possible, there’s therefore no term that should be used. It would, in fact, be wrong to call this cis, trans, E, or Z. When an alkene has two of the same substituent on the same side, there is only one unique configuration of that alkene, and so it cannot be called cis, trans, E, or Z.
    [Show full text]
  • Radical Hydroacylation of C-C and N-N Double Bonds in Air
    University College London Radical Hydroacylation of C-C and N-N Double Bonds in Air by Jenna Marie Ahern Submitted in partial fulfilment of the requirements for the degree of Doctor of Philosophy Declaration I, Jenna Marie Ahern, confirm that the work presented in this thesis is my own. Where information has been derived from other sources, I confirm that this has been indicated in the thesis. Jenna Marie Ahern October 2010 Radical Hydroacylation of C-C and N-N Double Bonds in Air Jenna Marie Ahern Abstract The formation of C-C and C-N bonds in modern organic synthesis is a key target for methodological advancement. Current methods of C-C and C-N bond formation often involve the use of expensive catalysts, or sub-stoichiometric reagents, which can lead to the generation of undesirable waste products. This thesis describes a novel and environmentally benign set of reaction conditions for the formation of C-C and C-N bonds by hydroacylation and this is promoted by mixing two reagents, an aldehyde and an electron-deficient double bond, under freely available atmospheric oxygen at room temperature Chapter 1 will provide an introduction to the thesis and mainly discusses methods for C-C bond formation, in particular, radical chemistry and hydroacylation. Chapter 2 describes the hydroacylation of vinyl sulfonates and vinyl sulfones (C-C double bonds) with aliphatic and aromatic aldehydes with a discussion and evidence for the mechanism of the transformation. Chapter 3 details the synthesis of precursors for intramolecular cyclisations and studies into aerobic intramolecular cyclisations. Chapter 4 describes the hydroacylation of vinyl phosphonates (C-C double bonds) and diazocarboxylates (N-N double bonds) with aliphatic and aromatic aldehydes bearing functional groups.
    [Show full text]
  • Development of Copper-Catalyzed Chemoselective Reactions
    Vol. 68, No. 5 Chem. Pharm. Bull. 68, 405–420 (2020) 405 Review Development of Copper-Catalyzed Chemoselective Reactions Yohei Shimiz u a,b a Department of Chemistry, Faculty of Science, Hokkaido University; Kita 10 Nishi 8, Kita-ku, Sapporo 060–0810, Japan: and b Institute for Chemical Reaction Design and Discovery (WPI- ICReDD), Hokkaido University; Kita 21 Nishi 10, Kita-ku, Sapporo 001–0021, Japan. Received August 30, 2019 Chemoselective reactions can contribute to streamlining synthesis of pharmaceuticals, agrochemicals, and other functional molecules by avoiding use of protecting groups. In this review, copper catalysts were demonstrated useful for developing two types of chemoselective reactions: C–C bond-forming reactions at an anomeric carbon of unprotected aldoses and difunctionalization reaction of C–C multiple bonds. The “soft” nucleophilic copper species exhibit orthogonal reactivity toward “hard” polar functional groups and prefer- entially react with “soft” functional groups. The catalysis also controls stereoselectivity and/or regioselectiv- ity to provide value-added products from readily available feedstock compounds. Key words chemoselective reaction; catalyst; copper; aldose; multiple bond; difunctionalization 1. Introduction carbon nucleophiles to develop chemoselective C–C bond- Biologically active molecules often possess multiple func- forming reactions. The soft organocopper species chemoselec- tional groups. Synthesis of these compounds requires protect- tively reacts with soft carbon electrophiles in the presence of ing groups to secure the promotion of intended transformation polar hard functional groups without protecting these possible at the particular functional group of the starting molecule. reactive sites. In this review we introduce two types of trans- The protecting groups, however, are not included in the final formations: C–C bond-forming reactions at anomeric position products.
    [Show full text]
  • M.Sc. Chemistry Syllabus
    SYLLABUS FOR MASTERS PROGRAMME (M.Sc.) IN CHEMISTRY (BATCH-2016 and BATCH-2017) UNDER CHOICE BASED CREDIT SYSTEM (CBCS) DEPARTMENT OF CHEMISTRY ISLAMIC UNIVERSITY OF SCIENCE AND TECHNOLOGY, AWANTIPORA, PULWAMA, KASHMIR, J&K, INDIA, 192122. Department of Chemistry Islamic University of Science and Technology Master’s Programme A Master’s Programme consists of a set of Core Courses and Optional Course. The entire course carries choice based credit system. A Master’s degree in Chemistry course is divided in to 04 semesters comprising 02 odd semesters and 02 even semesters. Credits The term credit is used to describe the quantum of syllabus for various programmes in terms and hours of study. It indicates differential weightage given according to the contents and duration of the courses in the curriculum design. Courses Each course may consist of Lectures/ Tutorials/ Laboratory work/ Seminar/ Project work/ Practical training report/ Viva voce etc. Subject Code Fixation The following code system (5 characters) is adopted for Post graduate course in chemistry PXX PG code for department X Course Type X Specification of that course Example PCH CC 101 PCH-CC-101 PG Code Core Course Specification of that course CC– Core Courses: Theory & Practical DCE – Discipline Centric OE-Open Electives Department of Chemistry Islamic University of Science and Technology Total Credit and Marks Distribution for the Four Semesters Course Type No of Papers Credits per Paper Total Credits Marks per Paper Total Marks Core Course 14 4 56 100 1400 (Theory) Core Course
    [Show full text]
  • Vicinal Difunctionalization of Carbonâ
    ARTICLE https://doi.org/10.1038/s41467-020-19748-z OPEN Vicinal difunctionalization of carbon–carbon double bond for the platform synthesis of trifluoroalkyl amines ✉ Ferenc Béke1, Ádám Mészáros1, Ágnes Tóth1, Bence Béla Botlik1 & Zoltán Novák 1 Regioselective vicinal diamination of carbon–carbon double bonds with two different amines is a synthetic challenge under transition metal-free conditions, especially for the synthesis of 1234567890():,; trifluoromethylated amines. However, the synthesis of ethylene diamines and fluorinated amine compounds is demanded, especially in the pharmaceutical sector. Herein, we demonstrate that the controllable double nucleophilic functionalization of an activated alkene synthon, originated from a trifluoropropenyliodonium salt with two distinct nucleophiles, enables the selective synthesis of trifluoromethylated ethylene amines and diamines on broad scale with high efficiency under mild reaction conditions. Considering the chemical nature of the reactants, our synthetic approach brings forth an efficient methodology and provides versatile access to highly fluorinated amines. 1 ELTE “Lendület” Catalysis and Organic Synthesis Research Group, Institute of Chemistry, Eötvös Loránd University, Pázmány Péter stny. 1/A, 1117 ✉ Budapest, Hungary. email: [email protected] NATURE COMMUNICATIONS | (2020) 11:5924 | https://doi.org/10.1038/s41467-020-19748-z | www.nature.com/naturecommunications 1 ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-020-19748-z he vicinal diamine backbone is a prevalent motif in natural free conditions has been presented with bifunctional nucleophiles products, chelating agents, chiral ligands, and pharma- in an intramolecular manner to afford N,N- and N,O-heterocyclic T 1,2 ceuticals . Nature presents this structural motif in the systems using alkenyl-sulfonium salts with two adjacent electro- form of non-proteinogenic amino acids which constitute the philic centers29–32.
    [Show full text]
  • Studies in Stereochemistry Donald Charles Best Iowa State University
    Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1968 Studies in stereochemistry Donald Charles Best Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Best, Donald Charles, "Studies in stereochemistry " (1968). Retrospective Theses and Dissertations. 3648. https://lib.dr.iastate.edu/rtd/3648 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. This dissertation has been microiilined exactly as received g 8"14.773 BEST, Donald Charles, 1940- STUDIES IN STEREOCHEMISTRY. Iowa State University, Ph,D., 1968 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan STUDIES IN STEREOCHEMISTRY by Donald Charles Best A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY Major Subject : Organic Chemistry Approved : Signature was redacted for privacy. Signature was redacted for privacy. Head of Major Department Signature was redacted for privacy. Iowa State University of Science and Technology Ames, Iowa 1968 il TABLE OF CONTENTS Page PART I: CONFORMATIONAL PREFERENCES OF ACYCLIC PIASTEREOMERS la HISTORICAL lb I RESULTS AND DISCUSSION 7 EXPERIMENTAL 48 PART II : SUBSTITUENT EFFECTS ON SUSPECTED PHENONIUM ION INTERMEDIATES 82; HISTORICAL R3 RESULTS AND DISCUSSION 94 ' EXPERIMENTAL 109 LITERATURE CITED 155 ACKNOWLEDGEMENTS l40 ' la PART I: CONFORMATIONAL PREFERENCES OF ACYCLIC DIASTEREOMERS lb HISTORICAL The subject of conformational analysis was introduced about seventy-five years ago by Sachse (49).
    [Show full text]
  • JUN I 13998 Scienct LIBRARIES This Doctoral Thesis Has Been Examined by a Committee of the Department of Chemistry As Follows
    THE DEVELOPMENT OF ORGANOTIN REAGENTS FOR ORGANIC SYNTHESIS by David Scott Hays B. S. Chemistry, University of Illinois Submitted to the Department of Chemistry in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY IN ORGANIC CHEMISTRY at the Massachusetts Institute of Technology June 1998 © Massachusetts Institute of Technology, 1998 All rights reserved Signature of Author Department of Chemistry May 14, 1998 Certified by Gregory C. Fu t' Thesis Supervisor Accepted by Dietmar Seyferth Chairman, Departmental Committee on Graduate Students JUN I 13998 scienct LIBRARIES This doctoral thesis has been examined by a committee of the Department of Chemistry as follows: Professor Peter H. Seeberger I_ _ /1 Chairman Professor Gregory C. Fu J _J Thesis Supervisor Professor Rick L. Danheiser THE DEVELOPMENT OF ORGANOTIN REAGENTS FOR ORGANIC SYNTHESIS by David Scott Hays Submitted to the Department of Chemistry on May 14, 1998 in partial fulfillment of the requirements for the Degree of Doctor of Philosophy at the Massachusetts Institute of Technology ABSTRACT A method for the intramolecular pinacol coupling of dialdehydes and ketoaldehydes is described. The method was found to be useful for synthesizing 1,2-cyclopentanediols with very high degrees of diastereoselectivity in favor of the cis stereochemistry. 1,2- Cyclohexanediols were generated with lower degrees of stereoselection. This free radical chain process involves as the key steps: 1) an intramolecular addition of a tin ketyl radical to a pendant carbonyl group, followed by 2) a rapid intramolecular homolytic displacement by an oxygen radical at the tin center to liberate an alkyl radical. The development of a Bu 3 SnH-catalyzed carbon-carbon bond forming reaction (the reductive cyclization of enals and enones) is described, followed by a catalytic variant of the Barton-McCombie deoxygenation reaction.
    [Show full text]
  • Alkenes and Alkynes I: Properties and Synthesis
    Chapter 7 Alkenes and Alkynes I: Properties and Synthesis. Elimination Reactions of Alkyl Halides Ch. 7 - 1 1. Introduction Alkenes ● Hydrocarbons containing C=C ● Old name: olefins CH2OH Vitamin A H3C H3C H H Cholesterol HO Ch. 7 - 2 Alkynes ● Hydrocarbons containing C≡C ● Common name: acetylenes H N O I Cl C O C O Cl F3C C Cl C Cl Efavirenz Haloprogin (antiviral, AIDS therapeutic) (antifungal, antiseptic) Ch. 7 - 3 2. The (E) - (Z) System for Designating Alkene Diastereomers Cis-Trans System ● Useful for 1,2-disubstituted alkenes ● Examples: H Br Cl Cl (1) Br vs H H H trans -1-Bromo- cis -1-Bromo- 2-chloroethene 2-chloroethene Ch. 7 - 4 ● Examples H (2) vs H H H trans -3-Hexene cis -3-Hexene Br (3) Br Br vs Br trans -1,3- cis -1,3- Dibromopropene Dibromopropene Ch. 7 - 5 (E) - (Z) System ● Difficulties encountered for trisubstituted and tetrasubstituted alkenes CH3 e.g. Cl cis or trans? Br H Cl is cis to CH3 and trans to Br Ch. 7 - 6 The Cahn-Ingold-Prelog (E) - (Z) Convention ● The system is based on the atomic number of the attached atom ● The higher the atomic number, the higher the priority Ch. 7 - 7 The Cahn-Ingold-Prelog (E) - (Z) Convention ● (E) configuration – the highest priority groups are on the opposite side of the double bond “E ” stands for “entgegen”; it means “opposite” in German ● (Z) configuration – the highest priority groups are on the same side of the double bond “Z ” stands for “zusammer”; it means “together” in German Ch.
    [Show full text]
  • As a Widely Applicable, Homogeneous Catalyst for Aerobic
    RESEARCH ARTICLE AEROBIC OXIDATION 2015 © The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. Distributed Silver(I) as a widely applicable, homogeneous under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC). catalyst for aerobic oxidation of aldehydes toward 10.1126/sciadv.1500020 carboxylic acids in water—“silver mirror”: From stoichiometric to catalytic Mingxin Liu, Haining Wang, Huiying Zeng, Chao-Jun Li* The first example of a homogeneous silver(I)-catalyzed aerobic oxidation of aldehydes in water is reported. More than 50 examples of different aliphatic and aromatic aldehydes, including natural products, were tested, and all of them successfully underwent aerobic oxidation to give the corresponding carboxylic acids in extremely high yields. The reaction conditions are very mild and greener, requiring only a very low silver(I) catalyst loading, using atmospheric oxygen as the oxidant and water as the solvent, and allowing gram-scale oxidation with only 2 mg of our catalyst. Chromatography is completely unnecessary for purification in most cases. Oxidation is a central task for organic chemists to achieve conversion of We began our investigation by introducing various silver(I) salts or different organic compounds. Among them, oxidation of aldehydes to complexes to benzaldehyde as a standard in air at atmospheric pressure give carboxylic acids is one of the most well-known and most frequently without a balloon in a sealed tube (Table 1). We found the efficiency of used methodologies (1, 2), for example, by stoichiometrically using the the transformation to be strongly affected by the presence of inorganic Cr(IV)-based Jones reagent (3, 4), the Ag(I)-based Tollen’s reaction (5), salt (for example, entries 1 and 2).
    [Show full text]