DOCSLIB.ORG

Organic Reactions in Aqueous Media with a Focus on Carbon−Carbon Bond Formations: a Decade Update

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Organic Reactions in Aqueous Media with a Focus on Carbon−Carbon Bond Formations: a Decade Update Chem. Rev. 2005, 105, 3095−3165 3095 Organic Reactions in Aqueous Media with a Focus on Carbon−Carbon Bond Formations: A Decade Update Chao-Jun Li Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Quebec H3A 2K6, Canada, and Department of Chemistry, Tulane University, New Orleans, Louisiana 70118 Received January 31, 2005 Contents 4.2.5. Hydrometalation/Coupling 3107 4.2.6. Pauson−Khand-Type Reactions 3108 1. Introduction 3096 4.2.7. Other Transition-Metal-Catalyzed 3108 2. Reaction of Alkanes 3096 Cyclization Reactions 3. Reaction of Alkenes 3097 4.2.8. Reductive Coupling 3109 3.1. Electrophilic Additions of Alkenes 3097 5. Reaction of Aromatic Compounds 3110 3.2. Radical Reactions of Alkenes 3097 5.1. Electrophilic Substitutions 3110 3.2.1. Radical Polymerization of Alkenes 3097 5.2. Radical Substitution 3111 3.2.2. Radical Additions 3098 5.3. Oxidative Coupling 3111 3.2.3. Radical Cyclization 3098 5.4. Photochemical Reactions 3111 3.3. Carbene Reactions 3098 3.3.1. The Generation of Carbenes in Aqueous 3098 6. Reaction of Carbonyl Compounds 3111 Media 6.1. Nucleophilic Additions 3111 3.3.2. The Stability of Carbenes 3098 6.1.1. Allylation 3111 3.3.3. The Reaction of Carbenes with Alkenes 3099 6.1.2. Propargylation 3120 in Aqueous Media 6.1.3. Benzylation 3121 3.4. Transition-Metal-Catalyzed Additions 3099 6.1.4. Arylation/Vinylation 3121 3.4.1. Polymerizations 3099 6.1.5. Alkynylation 3121 3.4.2. Heck Reactions and Related Vinylation/ 3099 6.1.6. Alkylation 3121 Arylation 6.1.7. Reformatsky-Type Reaction 3122 3.4.3. Hydrovinylation 3100 6.1.8. Direct Aldol Reaction 3122 3.4.4. Reaction with Arenes 3100 6.1.9. Mukaiyama Aldol Reaction 3124 3.4.5. Hydroformylation 3100 6.1.10. Hydrogen Cyanide Addition 3125 3.4.6. Reaction with Alkynes 3101 6.2. Pinacol Coupling 3126 3.4.7. Carbonylation 3101 6.3. Wittig Reactions 3126 3.5. Olefin Metathesis 3101 7. Reaction of R,â-Unsaturated Carbonyl 3127 3.5.1. Ring-Opening Metathesis Polymerization 3101 Compounds (ROMP) 7.1. Conjugate Additions 3127 3.5.2. Ring-Closing Metathesis (RCM) 3102 7.1.1. Addition of R-Carbonyl Compounds 3127 3.6. Cycloaddition Reactions of Alkenes and 3102 Conjugated Alkenes 7.1.2. Addition of Allyl Groups 3127 4. Reaction of Alkynes 3103 7.1.3. Addition of Alkyl Groups 3127 4.1. Reaction of Terminal Alkynes 3103 7.1.4. Addition of Vinyl and Aryl Groups 3128 4.1.1. Alkyne Oxidative Dimerization 3103 7.1.5. Other Conjugate Additions 3128 − 4.1.2. Alkyne Dimerization 3103 7.2. Baylis Hillman Reactions 3129 4.1.3. Reaction of Alkynes with Organic Halides 3103 7.3. Reductive Coupling 3129 d − t 4.1.4. Reaction of Alkynes with Carbonyl 3104 8. Reaction of C N, C N, and C N Compounds 3130 Compounds 8.1. Nucleophilic Additions 3130 4.1.5. Reaction with Imines 3104 8.1.1. Mannich-Type Reactions 3130 4.1.6. Conjugate Addition 3105 8.1.2. Addition of Allyl Groups 3131 4.2. Reaction of CtC Bonds 3105 8.1.3. Reaction with Propargyl Groups 3132 4.2.1. Nucleophilic Additions 3105 8.1.4. Addition of Alkyl Groups 3133 4.2.2. Electrophilic Addition 3106 8.1.5. Addition of Vinyl and Aryl Groups 3133 4.2.3. Hydrocarboxylation 3106 8.1.6. Other Nucleophilic Additions 3134 4.2.4. Hydrophosphinylation 3107 8.2. Reductive Coupling 3134 9. Reaction of Organic Halides 3134 * Fax: 514-398-3797. Tel: 514-3988457. E-mail: [email protected]. 10.1021/cr030009u CCC: $53.50 © 2005 American Chemical Society Published on Web 07/23/2005 3096 Chemical Reviews, 2005, Vol. 105, No. 8 Li 9.1. Nucleophilic Substitution 3134 9.2. Reductive Coupling 3135 9.2.1. Wurtz-Type Coupling 3135 9.2.2. Ullmann-Type Coupling and Related 3135 Reactions 9.3. Carbonylation of Organic Halides 3136 9.3.1. Carbonylation of Alkyl Halides 3136 9.3.2. Carbonylation of Allylic and Benzylic 3136 Halides 9.3.3. Carbonylation of Aryl Halides 3136 9.4. The Heck Coupling 3136 9.5. The Suzuki Coupling 3137 9.6. The Stille Coupling 3139 9.7. Other Couplings 3139 9.8. The Trost−Tsuji Reaction 3139 Chao-Jun Li was born in 1963 and received his B.Sc. at Zhengzhou 10. Pericyclic Reactions 3140 University, 1983, his M.S. at the Chinese Academy of Sciences in Beijing, 1988, and his Ph.D. at McGill University, 1992 (with T. H. Chan and D. 10.1. Diels−Alder Reactions 3140 N. Harpp). He spent 1992−1994 as a NSERC Postdoctoral Fellow in B. 10.1.1. Diels−Alder Reactions Promoted by 3140 M. Trost’s laboratory at Stanford University and became an assistant Water professor in 1994 at Tulane University. He was promoted to associate 10.1.2. Lewis-Acid-Catalyzed Reactions 3141 professor with tenure in 1998 and full professor in 2000. He was a visiting 10.1.3. Asymmetric Diels−Alder Reactions in 3143 faculty member (with Robert G. Bergman) at the University of California Water at Berkeley, 2002. In 2003, he became a Canada Research Chair (Tier 10.1.4. Theoretical Studies 3144 I) in Organic/Green Chemistry and a Professor of Chemistry at McGill University in Canada. His current research efforts are to develop innovative 10.1.5. Synthetic Applications 3145 and fundamentally new organic reactions that will defy conventional 10.2. Hetero-Diels−Alder Reactions 3147 reactivities and possess high “atom efficiency”. Widely known researches 10.2.1. Water-Promoted and Acid-Catalyzed 3147 include the development of Grignard-type reactions in water, transition- Reactions metal catalysis in air and water, alkyne−aldehyde−amine coupling (A3- − − 3 10.2.2. Asymmetric Hetero-Diels−Alder Reactions 3149 coupling), asymmetric alkyne aldehyde amine coupling (AA -coupling), and cross-dehydrogenative coupling (CDC) reactions. 10.3. Other Cyclization Reactions 3149 of Green Chemistry. While 10 years ago, the whole 10.3.1. Alder-ene Reactions 3149 field was a mere curiosity for only a few practitioners, 10.3.2. 1,3-Dipolar Cycloaddition Reactions 3150 now organic reactions in water have become some of 10.4. Sigmatropic Rearrangements 3150 the most exciting research endeavors. There have 10.4.1. Claisen Rearrangements 3150 been many excellent reviews on specific topics in this 10.4.2. Cope Rearrangements 3152 field.5 There has also been a great advance in 10.5. Photochemical Cycloaddition Reactions 3152 understanding the reactions of organic compounds 11. Conclusion 3153 in high-temperature water, which has broad implica- 12. Acknowledgment 3153 tions ranging from the origin of life and energy and 13. Note Added in Proof 3153 fuels to chemical synthesis.6 Several excellent reviews 7 14. References 3153 have been published on this subject. However, the current comprehensive review updates the progress of developing carbon-carbon bond formations in 1. Introduction aqueous media for synthetic purposes within the past Organic syntheses are composed of two main types decade (mostly prior to 2004). In addition, as the of reactions: Carbon-carbon bond formations and subject is so broad at the present time, it is necessary functional group transformations. C-C bond forma- to rearrange the topics based on functional group tion is the essence of organic synthesis1 and provides transformations, which is parallel to the classical the foundation for generating more complicated C-C bond formations in organic chemistry. More organic compounds from simpler ones. Although details on specific subjects can be obtained from enzymatic processes in nature must occur in an related reviews in the references. aqueous environment by necessity, water has been a solvent to be avoided for common organic reactions. 2. Reaction of Alkanes Since the pioneering studies of Diels-Alder reactions The direct functionalization of alkanes is the Holy by Breslow,2 there has been increasing recognition Grail of chemical synthesis and has fundamental that organic reactions can proceed well in aqueous implications in a variety of fields including chemicals, media and offer advantages over those occurring in energy, medicine, and the environment. While Na- organic solvents.3 A decade ago, the first comprehen- ture has used monohydrogenase and other enzymes sive review on carbon-carbon bond formations in to functionalize alkanes in aqueous environments at aqueous media was reported.4 At that time, only a ambient conditions,8 alkanes are generally considered few dozen references existed in the literature on this nonreactive in conventional organic chemistry. Clas- subject, with the exception of hydroformylation reac- sical reactions of alkanes are all under drastic tions. Since then, there has been an explosion of conditions. However, within the past two decades, research activities in this field, which has been significant progress has been made in the “activation” partially attributed to the development of the field of alkanes under milder conditions.9 Such activations Organic Reactions in Aqueous Media Chemical Reviews, 2005, Vol. 105, No. 8 3097 Table 1. Methane Carboxylation in Aqueous Solutiona using a cerium-salt-catalyzed cyclization in aqueous ionic liquids (eq 2).19 A further improvement on the tetrahydropyranol a Reprinted from ref 11 by permission of the Royal Society formation was made by using the Amberlite IR-120 of Chemistry. Plus resin, an acidic resin with a sulfonic acid moiety, in which a mixture of an aldehyde and homoallyl can be performed even in aqueous conditions,10 alcohol in water, in the presence of the resin and although a detailed discussion of the field is outside under sonication, yielded the desired tetrahydropy- 20 the scope of the current review. By far, most research ranol derivatives.
Load more

Recommended publications
  • Spirocyclic-2-Oxindoles from Morita-Baylis- Hillman Adduct of Isatin
    Synthesis of Functionalized 2-Oxindoles and 3- Spirocyclic-2-Oxindoles from Morita-Baylis- Hillman Adduct of Isatin THESIS SUBMITTED TO THE UNIVERSITY OF KERALA IN FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY IN CHEMISTRY UNDER THE FACULTY OF SCIENCE BY K. SELVAKUMAR ORGANIC CHEMISTRY SECTION NATIONAL INSTITUTE FOR INTERDISCIPLINARY SCIENCE AND TECHNOLOGY (CSIR) THIRUVANANTHAPURAM-695 019 KERALA, INDIA 2012 …To my beloved family DECLARATION I hereby declare that Ph. D. thesis entitled “Synthesis of Functionalized 2-Oxindoles and 3-Spirocyclic-2-Oxindoles from Morita-Baylis-Hillman Adduct of Isatin” is an independent work carried out by me and it has not been submitted anywhere else for any other degree, diploma or title. K. Selvakumar Thiruvananthapuram 2012 i CERTIFICATE This is to certify that the work embodied in the thesis entitled “Synthesis of Functionalized 2-Oxindoles and 3-Spirocyclic-2-Oxindoles from Morita- Baylis-Hillman Adduct of Isatin” has been carried out by Mr. K. Selvakumar under our combined supervision at the Chemical Sciences and Technology Division of National Institute for Interdisciplinary Science and Technology (CSIR), Thiruvananthapuram and the same has not been submitted elsewhere for any other degree. Dr. R. LUXMI VARMA Dr. P. SHANMUGAM (Thesis supervisor) (Thesis supervisor) Thiruvananthapuram ii ACKNOWLEDGEMENTS At the outset, I express my sincere and heartfelt gratitude to my research supervisor Dr. P. Shanmugam for suggesting me interesting research topic and for his care, constructive criticism and continuous support throughout my doctoral studies. I would like to offer special thanks to Dr. R. Luxmi Varma, Co-guide for her suggestions, encouragement and timely help during the tenure of this work.
    [Show full text]
  • Deoxydehydration of Vicinal Diols by Homogeneous Catalysts: a Mechanistic Overview
    Deoxydehydration of vicinal diols by homogeneous royalsocietypublishing.org/journal/rsos catalysts: a mechanistic overview Review Cite this article: DeNike KA, Kilyanek SM. 2019 Kayla A. DeNike and Stefan M. Kilyanek Deoxydehydration of vicinal diols by homogeneous catalysts: a mechanistic overview. Department of Chemistry and Biochemistry, University of Arkansas, 1 University of Arkansas, Fayetteville, AR 727001, USA R. Soc. open sci. 6: 191165. http://dx.doi.org/10.1098/rsos.191165 SMK, 0000-0002-6179-2510 Received: 4 July 2019 Deoxydehydration (DODH) is an important reaction for the Accepted: 4 October 2019 upconversion of biomass-derived polyols to commodity chemicals such as alkenes and dienes. DODH can be performed Subject Category: by a variety of early metal-oxo catalysts incorporating Re, Mo and V. The varying reduction methods used in the DODH Chemistry catalytic cycle impact the product distribution, reaction Subject Areas: mechanism and the overall yield of the reaction. This review surveys the reduction methods commonly used in homogeneous inorganic chemistry/organometallic chemistry/ DODH catalyst systems and their impacts on yield and reaction green chemistry conditions. Keywords: deoxydehydration, catalysis, biomass upconversion, early metal-oxo 1. Introduction Due to the long-term implications for the climate of continuing to Author for correspondence: consume non-renewable carbon resources, such as oil, the Stefan M. Kilyanek decarbonization of the economy has become the topic of e-mail: [email protected] significant public and scientific concern [1,2]. As a result, the development of processes to produce valuable carbon-based commodity chemicals from renewable carbon feedstocks has become an important field of study [3].
    [Show full text]
  • The Arene–Alkene Photocycloaddition
    The arene–alkene photocycloaddition Ursula Streit and Christian G. Bochet* Review Open Access Address: Beilstein J. Org. Chem. 2011, 7, 525–542. Department of Chemistry, University of Fribourg, Chemin du Musée 9, doi:10.3762/bjoc.7.61 CH-1700 Fribourg, Switzerland Received: 07 January 2011 Email: Accepted: 23 March 2011 Ursula Streit - [email protected]; Christian G. Bochet* - Published: 28 April 2011 [email protected] This article is part of the Thematic Series "Photocycloadditions and * Corresponding author photorearrangements". Keywords: Guest Editor: A. G. Griesbeck benzene derivatives; cycloadditions; Diels–Alder; photochemistry © 2011 Streit and Bochet; licensee Beilstein-Institut. License and terms: see end of document. Abstract In the presence of an alkene, three different modes of photocycloaddition with benzene derivatives can occur; the [2 + 2] or ortho, the [3 + 2] or meta, and the [4 + 2] or para photocycloaddition. This short review aims to demonstrate the synthetic power of these photocycloadditions. Introduction Photocycloadditions occur in a variety of modes [1]. The best In the presence of an alkene, three different modes of photo- known representatives are undoubtedly the [2 + 2] photocyclo- cycloaddition with benzene derivatives can occur, viz. the addition, forming either cyclobutanes or four-membered hetero- [2 + 2] or ortho, the [3 + 2] or meta, and the [4 + 2] or para cycles (as in the Paternò–Büchi reaction), whilst excited-state photocycloaddition (Scheme 2). The descriptors ortho, meta [4 + 4] cycloadditions can also occur to afford cyclooctadiene and para only indicate the connectivity to the aromatic ring, and compounds. On the other hand, the well-known thermal [4 + 2] do not have any implication with regard to the reaction mecha- cycloaddition (Diels–Alder reaction) is only very rarely nism.
    [Show full text]
  • United States Patent (19) 11 Patent Number: 5,342,985 Herrmann Et Al
    USOO5342985A United States Patent (19) 11 Patent Number: 5,342,985 Herrmann et al. (45. Date of Patent: Aug. 30, 1994 54) ORGANIC DERIVATIVES OF RHENIUM 58 Field of Search ................ 556/482, 485; 560/130, OXDES AND THER PREPARATION AND 560/219, 221, 205; 568/626, 627, 630, 655, 685, USE FOR THE METATHESS OF OLEFENS 687; 570/135, 136; 585/510,520 75 Inventors: Wolfgang A. Herrmann, Freising: Primary Examiner-Paul F. Shaver Werner Wagner, Munich; Ursula Attorney, Agent, or Firm-Connolly & Hutz Volkhardt, Freising, all of Fed. Rep. of Germany 57 ABSTRACT 73) Assignee: Hoechst AG, Frankfurt am Main, The invention relates to a process for the metathesis of Fed. Rep. of Germany olefins which comprises reacting an olefin of the for mula YCZ=CZ-(CX2),R2 (II) wherein 21 Appl. No.: 569,614 n is an integer from 1 to 28, 22 Filed: Aug. 20, 1990 X represents H or F, Y represents H or alkyl having from 1 to 10 carbon Related U.S. Application Data atoms and 63 Continuation-in-part of Ser. No. 320,404, Mar. 8, 1989, Z represents Hor a non-aromatic hydrocarbon group abandoned. having from 1 to 6 carbon atoms and R2 represents a H, alkyl, halogen, COOR3 or OR', wherein R3and 30 Foreign Application Priority Data R4 represent alkyl having from 1 to 15 carbon Dec. 10, 1988 DE Fed. Rep. of Germany ....... 384,733 atoms or phenyl which is unsubstituted or contains Jan. 31, 1989 IDE Fed. Rep. of Germany ....... 3902787 from 1 to 3 substituents or wherein R is trialkylsi Mar.
    [Show full text]
  • Hybrid Macrocycle Formation and Spiro Annulation on Cis-Syn-Cis-Tricyclo[6.3.0.02,6]Undeca-3,11-Dione and Its Congeners Via Ring-Closing Metathesis
    Hybrid macrocycle formation and spiro annulation on cis-syn-cis-tricyclo[6.3.0.02,6]undeca-3,11-dione and its congeners via ring-closing metathesis Sambasivarao Kotha*, Ajay Kumar Chinnam and Rashid Ali Full Research Paper Open Access Address: Beilstein J. Org. Chem. 2015, 11, 1123–1128. Department of Chemistry, Indian Institute of Technology-Bombay, doi:10.3762/bjoc.11.126 Powai, Mumbai-400 076, India, Fax: 022-2572 7152 Received: 23 February 2015 Email: Accepted: 23 June 2015 Sambasivarao Kotha* - [email protected] Published: 06 July 2015 * Corresponding author This article is part of the Thematic Series "Progress in metathesis chemistry II". Keywords: aza-polyquiananes; Fischer indolization; macrocycles; ring-closing Guest Editor: K. Grela metathesis; spiropolyquinanes © 2015 Kotha et al; licensee Beilstein-Institut. License and terms: see end of document. Abstract We have developed a simple methodology to transform cis-syn-cis-triquinane derivative 2 into the diindole based macrocycle 6 involving Fischer indolization and ring-closing metathesis (RCM). Various spiro-polyquinane derivatives have been assembled via RCM as a key step. Introduction Design and synthesis of polyquinanes is an active area of variety of plant alkaloids (e.g., reserpine, strychnine, physostig- research during the last three decades [1-10]. Various theoreti- mine) and several important drugs contain indole as a key cally interesting as well as biologically active molecules such as component [29-32]. Therefore, we are interested in designing dodecahedrane, [5.5.5.5]fenestrane and retigeranic acid A new strategies to hybrid molecules containing both quinane and contain the quinane framework in their structures (Figure 1).
    [Show full text]
  • Photochemical Reactions As Key Steps in Natural Product Synthesis Thorsten Bach* and JRg P
    Reviews T. Bach and J. P. Hehn DOI: 10.1002/anie.201002845 Synthetic Methods Photochemical Reactions as Key Steps in Natural Product Synthesis Thorsten Bach* and Jrg P. Hehn Keywords: Dedicated to Professor David A. Evans cyclization · cycloaddition · on the occasion of his 70th birthday natural products · photochemistry · total synthesis Angewandte Chemie 1000 www.angewandte.org 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2011, 50, 1000 – 1045 Photochemical Reactions Photochemical reactions contribute in a significant way to the existing From the Contents repertoire of carbon–carbon bond-forming reactions by allowing access to exceptional molecular structures that cannot be obtained by 1. Introduction 1001 conventional means. In this Review, the most important photochemical 2. Photocyclizations 1001 transformations that have been employed in natural product synthesis are presented. Selected total syntheses are discussed as examples, with 3. Norrish–Yang Cyclizations 1008 particular attention given to the photochemical key step and its ste- reoselectivity. The structural relationship between the photochemically 4. Norrish Type I Cleavage Reactions 1009 generated molecule and the natural product is shown, and, where necessary, the consecutive reactions in the synthesis are illustrated and 5. Photochemical classified. Rearrangements 1011 6. Reactions via Dienol Intermediates 1015 1. Introduction 7. Patern–Bchi Reaction 1017 Is there anything that hasnt already been said or written about natural product synthesis?[1] Great art has been seen in 8. [2+2] Photocycloadditions of it,[2] and attempts have been made to establish it as a Olefins 1018 handcraft. Economical rules have been assigned to it,[3] and it has been fitted into logical schemes.[4] Some people view 9.
    [Show full text]
  • 4.3.6 Strain Energies and Heats of Formation
    Results and Discussion • 183 ∆ –1 dramatically reduces the barrier to inversion ( Eplan drops from 58.6 to 7.4 kJ mol ). This might partly reflect the dramatic reduction in the energy difference between ‘pla- ∆ nar’ and tetrahedral-like structures for neopentane and spiropentane ( EPT = 880 and 440 kJ mol–1, respectively) (see Section 4.3.2). The introduction of a pair of methylene bridges between the caps then reduces this barrier to zero, giving a broadened potential energy well with an equilibrium structure with D2h symmetry. 4.3.6 Strain Energies and Heats of Formation Determining the total strain energies (SEs) of our novel hydrocarbons allows for a comparison with other strained hydrocarbons.43 We have chosen to use a method of cal- culating strain energies which has been used to great effect by Schulman and Disch.32 This method determines the strain energy as the negative of the calculated enthalpy change of a homodesmic reaction in which the number of quaternary (C), tertiary (CH) and secondary (CH2) carbons present in the target hydrocarbon are balanced with prod- uct neopentane, isobutane and propane molecules. The number of primary (CH3) car- bons on each side of the reaction is then balanced using ethane. This preserves the number and type of C–C bonds on each side of the reaction and is found to give good cancellation of errors when the MP2 method is used to calculate energies (see also Section 3.2 on page 97). If these product molecules are defined as being strain free (which is usual), the enthalpy change of this homodesmic reaction gives the total strain of the target hydrocarbon.
    [Show full text]
  • Organic Molecules with Abnormal Geometric Parameters
    Russian Chemical Reviews 70 (12) 991 ± 1016 (2001) # 2001 Russian Academy of Sciences and Turpion Ltd DOI 10.1070/RC2001v070n12ABEH000633 Organic molecules with abnormal geometric parameters I V Komarov Contents I. Introduction 991 II. Stability of strained molecules 992 III. Abnormally long and short C7C bonds 993 IV. Elongated and shortened C=C bonds 995 V. Variations of the triple carbon ± carbon bond lengths in organic compounds 995 VI. Distortions of bond angles at the tetrahedral carbon atom 996 VII. Distortions of bond and torsion angles at the double bond in alkenes 1001 VIII. Distortions of the bond and torsion angles in the molecules of aromatic compounds 1005 IX. Distortions of cumulated double bonds 1008 X. Bending of the X17C:C7X2 fragment 1010 Abstract. Organic molecules, the structural parameters of which Table 1. Typical (averaged) lengths of some carbon ± carbon bonds. (carbon ± carbon bond lengths, bond and torsion angles) differ appreciably from the typical most frequently encountered values, Type of bond Length /A are discussed. Using many examples of `record-breaking' mole- cules, the limits of structural distortions in carbon compounds and Single bond their unusual chemical properties are demonstrated. Particular 3 3 attention is devoted to strained compounds not yet synthesised C sp 7C sp 1.53 3 2 whose properties have been predicted using quantum-chemical C sp 7C sp 1.51 3 calculations. Factors that ensure the stability of such compounds C sp 7C sp 1.47 2 2 are outlined. The bibliography includes 358 references. C sp 7C sp 1.48 C sp7C sp 1.38 I.
    [Show full text]
  • Copyrighted Material
    JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm SUBJECT INDEX The vast use of transition metal catalysts in organic chemistry makes the citation of every individual metal impractical, so there are limited citations of individual metals. Palladium is one exception where individual citations are common, in keeping with the widespread use of that metal. However, in most cases, the term metal catalyst, or catalyst, metal is used as a heading, usually representing transition metals. A-SE2 mechanism 893 and the steering wheel model acceleration of Diels-Alder reactions 487 151–152 reactions, high pressure A1 mechanism, acetal hydrolysis and universal NMR database 1038 487 155 hydrogen-bonding 1038 A1,3-strain 196 Cahn-Ingold-Prelog system hydrophobic effect 1038 A2 mechanism, acetal hydrolysis 149–152 in water 1038 487 determination 152 ionic liquids 1038 ab initio calculations 36 D/L nomenclature 149 micellular effects 1038 and acidity 346 Kishi’s NMR method 155 microwave irradiation 1038 and antiaromaticity 71 sequence rules 149–152 phosphate 1039 and nonclassical carbocations absolute hardness 64, 359, 361 solid state 1038 427 table 361 ultracentrifuge 1038 norbornyl carbocation 436 absorbents, chiral 168 ultrasound 1038 ab initio studies 248 absorption, and conjugation 317 zeolites 1038 1,2-alkyl shifts in alkyne anions differential, and diastereomers acceleration, Petasis reaction 1349 168 1202 and cubyl carbocation 413 differential, and resolution 169 acenaphthylene, reaction with and SN2 408–409 abstraction,
    [Show full text]
  • Design of Novel Well-Defined Organorhenium Heterogeneous Catalyst for Unsaturated Fatty Acid Derivatives Self-Metathesis
    Design of novel well-defined organorhenium heterogeneous catalyst for unsaturated fatty acid derivatives self-metathesis Thèse Abdelnasser Abidli Doctorat en sols et environnement Philosophiae Doctor (Ph.D.) Québec, Canada © Abdelnasser Abidli, 2015 Résumé La formation des liaisons C-C est parmi les cibles les plus élevés de la science et de la technologie de la catalyse. Dans ce cadre, la réaction de métathèse catalytique a gagné une importance considérable en raison de l'efficacité du processus de transformation. Par conséquent, un grand progrès a été réalisé dans ce domaine avec le développement de plusieurs catalyseurs homogènes et hétérogènes, ainsi que les différentes approches de métathèse. Cette formule a permis une conception plus facile et plus durable de diverses stratégies de synthèse dans différents domaines, y compris la synthèse organique, la science des polymères, etc. Cependant, le développement des catalyseurs de métathèse robustes pour les applications à grande échelle est encore une tâche difficile. Tenant compte de cela, les résultats de recherche présentés dans cette thèse de doctorat se concentrent sur la synthèse d'un nouveau catalyseur hétérogène de métathèse. Par conséquent, le méthyltrioxorhénium (MTO) a été supporté sur différents matériaux à base d'alumine. La performance des catalyseurs synthétisés a été étudié par l'auto-métathèse de l'oléate de méthyle, choisi comme substrat modèle; volumineux et fonctionnalisé, afin d'évaluer la tolérance des espèces actives aux groupements fonctionnels, ainsi que d'évaluer sa diffusion à l'intérieur des canaux mésoporeux. Tout d'abord, des supports très organisés à base alumine mésoporeux organisée modifiée avec le chlorure de zinc (ZnCl2-AMO) ont été préparés avec succès grâce à un procédé sol-gel puis une imprégnation post-synthèse.
    [Show full text]
  • Amido Rhenium Trioxides: Cases of Hindered Agostic CH
    Amido Rhenium Trioxides: Cases of Hindered Agostic C-H... M Interactions? Paul Benndorf,[a] Michael T. Gamer,[a] Peter W. Roesky,*[a] Georg Eickerling* [b] and Wolfgang Scherer*[b] _________________________ [a] Prof. Dr. P. W. Roesky, Dipl.-Chem. P. Benndorf, Dr. M. Gamer Institut für Anorganische Chemie Universität Karlsruhe (TH) Engesserstr. 15, 76131 Karlsruhe (Deutschland) Fax: (+49)721-608-4854 E-mail: [email protected] [b] Prof. Dr. W. Scherer, Dr. G. Eickerling Institut für Physik Lehrstuhl für Chemische Physik und Materialwissenschaften Universität Augsburg, 86135 Augsburg (Deutschland) Fax: (+49)821-598-3227 E-mail: [email protected] Supporting information for this article is available from the author 1 Abstract. The amido rhenium trioxides of composition ( iPr2N)ReO 3, ( iPrCyN)ReO 3 and (Cy 2N)ReO 3 (Cy = cyclohexyl) were synthesized in a one pot reaction starting from Re 2O7, Me 3SiCl and the corresponding amines ( iPr) 2NH, ( iPr)(Cy)NH, and (Cy) 2NH, respectively. Even two of the three compounds are high viscous oils or waxes at room temperature single crystals could be obtained at low temperatures and the solid state structures were established by single crystal X-ray diffraction. In the solid state the amido ligands of all three complexes are asymmetrically coordinated to the ReO 3 core allowing for one short Re …H-C contact in each case which might indicate the presence of β-agostic interaction. However, analysis of the charge density distribution provided us clear-cut criteria that β-agostic interactions are suppressed by the trans -influence of the oxo-groups.
    [Show full text]
  • Synthesis of Cyclic Α, Β-Unsaturated Ketones Via a Divergent Aldehyde Allylation and Ring-Closing Metathesis Method
    α β α β- Adam Kafal Master of Science Department of Chemistry University of Toronto 2011 Montmorillonite-catalyzed allylation of aldehydes with potassium allyltrifluoroborate is a convenient method for the synthesis of homoallylic alcohols. This chemistry was applied to various unsaturated aldehydes, and the homoallylic alcohols produced were used as common intermediates for two separate but related synthetic routes to -unsaturated ketones. In the first route, oxidation of the alcohol to the ketone was followed by base-catalyzed isomerization of the olefin to the -unsaturated ketone. This was subjected to ring closing metathesis conditions to afford the cyclic enone of ring size n. In the other route, ring-closing metathesis was performed first, followed by oxidation of the alcohol and isomerization of the olefin to the cyclic enone of ring size n+1. ii To the Batey lab: To Prof. Rob Batey, for accepting me into his lab, maintaining a firm but calm demeanour in the face of my periodic spells of incompetence, and ultimately teaching me more about chemistry than anyone ever has. None of this work or what it represents would have been possible without him. To Farhad Nowrouzi, for his staggering chemical know-how and assistance, and his exceptional irreverence; To Andy Tjeng, for being a voice of reason and calmness in an otherwise crass social environment, and for delicious moon cake; To Tim Ramadhar, for late-night 1980‘s hitdowns, and for taking a joke like a champ; To John Jantezko, for checking in and offering me help more often than I deserved; To Dr. Alejandro Castro, for starting this project, and for having one of the greatest accents I‘ve heard; To Alan Nhieu, for being a solid workout partner, and for bringing the party; To Dr.
    [Show full text]