2 Results and Discussion
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Supporting Information
Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2021 Supporting Information Synthesis, Oligomerization and Catalytic Studies of a Redox- Active Ni4-Cubane: A detailed Mechanistic Investigation Saroj Kumar Kushvaha, a† Maria Francis, b† Jayasree Kumar, a Ekta Nag, b Prathap Ravichandran, a b a Sudipta Roy* and Kartik Chandra Mondal* aDepartment of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India. bDepartment of Chemistry, Indian Institute of Science Education and Research (IISER) Tirupati 517507, India. † Both authors contributed equally. Table of Contents 1. General remarks 2. Syntheses of complexes 1-3 3. Detail characterization of complexes 1-3 4. Computational details 5. X-ray single crystal diffraction of complexes 1-3. 6. Details of catalytic activities of complex 3 6.1. General procedures for the syntheses of aromatic heterocycles (6) and various diazoesters (7) 6.2. Optimization of reaction condition for cyclopropanation of aromatic heterocycles (6) 6.3. General synthetic procedure and characterization data for cyclopropanated aromatic heterocycles (8) 6.4. Determination of relative stereochemistry of 8 7. 1H and 13C NMR spectra of compounds 8a-j 8. Mechanistic investigations and mass spectrometric analysis 9. References S1 1. General remarks All catalytic reactions were performed under Argon atmosphere. The progress of all the catalytic reactions were monitored by thin layer chromatography (TLC, Merck silica gel 60 F 254) upon visualization of the TLC plate under UV light (250 nm). Different charring reagents, such as phosphomolybdic acid/ethanol, ninhydrin/acetic acid solution and iodine were used to visualize various starting materials and products spots on TLC plates. -
Gold-Catalyzed Ethylene Cyclopropanation
Gold-catalyzed ethylene cyclopropanation Silvia G. Rull, Andrea Olmos* and Pedro J. Pérez* Full Research Paper Open Access Address: Beilstein J. Org. Chem. 2019, 15, 67–71. Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, doi:10.3762/bjoc.15.7 CIQSO-Centro de Investigación en Química Sostenible and Departamento de Química, Universidad de Huelva, Campus de El Received: 17 October 2018 Carmen 21007 Huelva, Spain Accepted: 11 December 2018 Published: 07 January 2019 Email: Andrea Olmos* - [email protected]; Pedro J. Pérez* - This article is part of the thematic issue "Cyclopropanes and [email protected] cyclopropenes: synthesis and applications". * Corresponding author Guest Editor: M. Tortosa Keywords: © 2019 Rull et al.; licensee Beilstein-Institut. carbene transfer; cyclopropane; cyclopropylcarboxylate; ethylene License and terms: see end of document. cyclopropanation; ethyl diazoacetate; gold catalysis Abstract Ethylene can be directly converted into ethyl 1-cyclopropylcarboxylate upon reaction with ethyl diazoacetate (N2CHCO2Et, EDA) F F in the presence of catalytic amounts of IPrAuCl/NaBAr 4 (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene; BAr 4 = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate). Introduction Nowadays the olefin cyclopropanation through metal-catalyzed carbene transfer starting from diazo compounds to give olefins constitutes a well-developed tool (Scheme 1a), with an exquisite control of chemo-, enantio- and/or diastereoselectiv- ity being achieved [1,2]. Previous developments have involved a large number of C=C-containing substrates but, to date, the methodology has not been yet employed with the simplest olefin, ethylene, for synthetic purposes [3]. Since diazo compounds bearing a carboxylate substituent are the most Scheme 1: (a) General metal-catalyzed olefin cyclopropanation reac- commonly employed carbene precursors toward olefin cyclo- tion with diazo compounds. -
Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc
Metal-Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc Richard H. Duncan Lyngdoh*,a, Henry F. Schaefer III*,b and R. Bruce King*,b a Department of Chemistry, North-Eastern Hill University, Shillong 793022, India B Centre for Computational Quantum Chemistry, University of Georgia, Athens GA 30602 ABSTRACT: This survey of metal-metal (MM) bond distances in binuclear complexes of the first row 3d-block elements reviews experimental and computational research on a wide range of such systems. The metals surveyed are titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc, representing the only comprehensive presentation of such results to date. Factors impacting MM bond lengths that are discussed here include (a) n+ the formal MM bond order, (b) size of the metal ion present in the bimetallic core (M2) , (c) the metal oxidation state, (d) effects of ligand basicity, coordination mode and number, and (e) steric effects of bulky ligands. Correlations between experimental and computational findings are examined wherever possible, often yielding good agreement for MM bond lengths. The formal bond order provides a key basis for assessing experimental and computationally derived MM bond lengths. The effects of change in the metal upon MM bond length ranges in binuclear complexes suggest trends for single, double, triple, and quadruple MM bonds which are related to the available information on metal atomic radii. It emerges that while specific factors for a limited range of complexes are found to have their expected impact in many cases, the assessment of the net effect of these factors is challenging. -
Catalytic Cyclopropanation of Polybutadienes
Erschienen in: Journal of Polymer Science, Part A: Polymer Chemistry ; 48 (2010), 20. - S. 4439-4444 https://dx.doi.org/10.1002/pola.24231 Catalytic Cyclopropanation of Polybutadienes JUAN URBANO,1 BRIGITTE KORTHALS,2 M. MAR DI´AZ-REQUEJO,1 PEDRO J. PE´ REZ,1 STEFAN MECKING2 1Laboratorio de Cata´ lisis Homoge´ nea, Departamento de Quı´mica y Ciencia de los Materiales, Unidad Asociada al CSIC, Centro de Investigacio´ n en Quı´mica Sostenible, Campus de El Carmen s/n, Universidad de Huelva, 21007 Huelva, Spain 2Department of Chemistry, University of Konstanz, 78464 Konstanz, Germany ABSTRACT: Catalytic cyclopropanation of commercial 1,2- or 1,4- bonyl-cyclopropene)]. Catalytic hydrogenation of residual dou- cis-polybutadiene, respectively, with ethyl diazoacetate catalyzed ble bonds of partially cyclopropanated polybutadienes provided by [TpBr3Cu(NCMe)] (TpBr3 ¼ hydrotris(3,4,5-tribromo-1-pyrazo- access to the corresponding saturated polyolefins. Thermal lyl)borate) at room temperature afforded high molecular weight properties are reported. 5 À1 (Mn > 10 mol ) side-chain or main-chain, respectively, carbox- yethyl cyclopropyl-substituted polymers with variable and con- trolled degrees of functionalization. Complete functionalization KEYWORDS: carbene addition; catalysis; functionalization of poly- of 1,4-cis-polybutadiene afforded poly[ethylene-alt-(3-ethoxycar- mers; organometallic catalysis; polar groups; polybutadienes INTRODUCTION Catalytic insertion polymerization of ethyl- polypropylene.6 Examples of catalytic post-polymerization ene and propylene is employed for the production of more reactions on saturated polyolefins are rare. The oxyfunction- than 60 million tons of polyolefins annually.1 These poly- alization of polyethylenes and polypropylenes by metal- mers are hydrocarbons, without any heteroatom-containing based catalysts can afford hydroxyl groups.7 We have functional groups, such as for example ester moieties. -
Recent Progress in the Synthetic Assembly of 2-Cyclopentenones
REVIEW ▌1 Recentreview Progress in the Synthetic Assembly of 2-Cyclopentenones David2-Cyclopentenone J. Synthesis Aitken,*a Hendrik Eijsberg,a,b Angelo Frongia,b Jean Ollivier,a Pier Paolo Pirasb a Laboratoire de Synthèse Organique & Méthodologie, ICMMO (CNRS UMR 8182), Université Paris Sud, 15 rue Georges Clemenceau, 91045 Orsay cedex, France Fax +33(1)69156278; E-mail: [email protected] b Dipartimento di Scienze Chimiche e Geologiche, Università degli studi di Cagliari, Complesso Universitario di Monserrato, S.S. 554, Bivio per Sestu, 09042 Monserrato, Cagliari, Italy Received: 09.07.2013; Accepted after revision: 21.08.2013 considerable number of ways in which the target ring sys- Abstract: An overview of the most important synthetic strategies currently available for the preparation of cyclopent-2-enones is pre- tem can be created from acyclic precursors, in either inter- sented and illustrated with recent applications. molecular or intramolecular mode. Most of the possible disconnection strategies have been examined, and it is im- 1 Introduction portant to recognize that for any given target 2-cyclopen- 2 Multicomponent Ring Assembly tenone, there may be several convenient approaches 3 Cyclizations available. The main approaches for ring construction are 4 Transformations of Existing Cyclic Systems summarized graphically in Figure 1. 5 Miscellaneous Methods O (4+1) O O (3+2) (3+2) coupling 6 Conclusions 1 1 1 5 5 2 5 2 2 RCM Key words: cyclopentenones, cyclization, carbocycles, ring clo- (4+1) (3+2) Rautenstrauch 4 3 4 3 4 3 aldol-type annulation sure, rearrangement, annulation (2+2+1) PKR Nazarov (3+2) Figure 1 The main ring-construction strategies for 2-cyclopente- none synthesis, showing the atom connectivities made during ring as- 1 Introduction sembly (left and center) and cyclization approaches (right). -
Appendix I: Named Reactions Single-Bond Forming Reactions Co
Appendix I: Named Reactions 235 / 335 432 / 533 synthesis / / synthesis Covered in Covered Featured in problem set problem Single-bond forming reactions Grignard reaction various Radical couplings hirstutene Conjugate addition / Michael reaction strychnine Stork enamine additions Aldol-type reactions (incl. Mukaiyama aldol) various (aldol / Claisen / Knoevenagel / Mannich / Henry etc.) Asymmetric aldol reactions: Evans / Carreira etc. saframycin A Organocatalytic asymmetric aldol saframycin A Pseudoephedrine glycinamide alkylation saframycin A Prins reaction Prins-pinacol reaction problem set # 2 Morita-Baylis-Hillman reaction McMurry condensation Gabriel synthesis problem set #3 Double-bond forming reactions Wittig reaction prostaglandin Horner-Wadsworth-Emmons reaction prostaglandin Still-Gennari olefination general discussion Julia olefination and heteroaryl variants within the Corey-Winter olefination prostaglandin Peterson olefination synthesis Barton extrusion reaction Tebbe olefination / other methylene-forming reactions tetrodotoxin hirstutene / Selenoxide elimination tetrodotoxin Burgess dehydration problem set # 3 Electrocyclic reactions and related transformations Diels-Alder reaction problem set # 1 Asymmetric Diels-Alder reaction prostaglandin Ene reaction problem set # 3 1,3-dipolar cycloadditions various [2,3] sigmatropic rearrangement various Cope rearrangement periplanone Claisen rearrangement hirstutene Oxidations – Also See Handout # 1 Swern-type oxidations (Swern / Moffatt / Parikh-Doering etc. N1999A2 Jones oxidation -
UNIVERSITY of CALIFORNIA Santa Barbara Regiochemistry of Nitroso
UNIVERSITY OF CALIFORNIA Santa Barbara Regiochemistry of Nitroso Hetero Diels-Alder Reactions, Catechol Siderophore Analogues for Surface Wet Adhesion, and an Inquiry-Based Synthetic Organic Laboratory Course A dissertation submitted in partial satisfaction of the requirements for the degree Doctor of Philosophy in Chemistry by Robert Bradley Lewis Committee in charge: Professor Alison Butler, Co-Chair Professor Javier Read de Alaniz, Co-Chair Professor R. Daniel Little Dr. Morgan Gainer, Lecturer January 2018 The dissertation of Robert Bradley Lewis is approved. ____________________________________________ R. Daniel Little ____________________________________________ Morgan Gainer ____________________________________________ Javier Read de Alaniz, Committee Co-Chair ____________________________________________ Alison Butler, Committee Co-Chair January 2018 Regiochemistry of Nitroso Hetero Diels-Alder Reactions, Catechol Siderophore Analogues for Surface Wet Adhesion, and an Inquiry-Based Synthetic Organic Laboratory Course Copyright © 2018 by Robert Bradley Lewis iii Acknowledgements When I decided to pursue my PhD in chemistry, I had no idea how much of a monumental undertaking it would be. It has been a long and difficult journey, and this dissertation only gives a brief glimpse of what went into the process. Nothing contained in this dissertation would possible without the continued support of all my family, friends, and co-workers. First and foremost, I want to thank my advisors and mentors. Javier Read de Alaniz, you gave me my first home at UCSB. You were always patient and caring, and you fostered a wonderful group environment, both in and out of the lab. Alison Butler, you gave me my second home at UCSB. Your unbridled enthusiasm for science is infectious and I appreciate that you allowed me to explore my interest in education by taking a few quarters to teach a lecture course. -
Basic Research Needs for Catalysis Science
Basic Research Needs for Catalysis Science Report of the Basic Energy Sciences Workshop on Basic Research Needs for Catalysis Science to Transform Energy Technologies May 8–10, 2017 Image courtesy of Argonne National Laboratory. DISCLAIMER This report was prepared as an account of a workshop sponsored by the U.S. Department of Energy. Neither the United States Government nor any agency thereof, nor any of their employees or officers, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of document authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. Copyrights to portions of this report (including graphics) are reserved by original copyright holders or their assignees, and are used by the Government’s license and by permission. Requests to use any images must be made to the provider identified in the image credits. This report is available in pdf format at https://science.energy.gov/bes/community-resources/reports/ REPORT OF THE BASIC RESEARCH NEEDS WORKSHOP FOR CATALYSIS SCIENCE Basic Research Needs for Catalysis Science TO TRANSFORM ENERGY TECHNOLOGIES Report from the U.S. Department of Energy, Office of Basic Energy Sciences Workshop May 8–10, 2017, in Gaithersburg, Maryland CHAIR: ASSOCIATE CHAIRS: Carl A. -
Cyclopropanation Catalyzed by Osmium Porphyrin Complexes Daniel A
Ames Laboratory Publications Ames Laboratory 3-1993 Cyclopropanation Catalyzed by Osmium Porphyrin Complexes Daniel A. Smith Iowa State University David N. Reynolds Iowa State University L. Keith Woo Iowa State University, [email protected] Follow this and additional works at: http://lib.dr.iastate.edu/ameslab_pubs Part of the Chemistry Commons The ompc lete bibliographic information for this item can be found at http://lib.dr.iastate.edu/ ameslab_pubs/362. For information on how to cite this item, please visit http://lib.dr.iastate.edu/ howtocite.html. This Article is brought to you for free and open access by the Ames Laboratory at Iowa State University Digital Repository. It has been accepted for inclusion in Ames Laboratory Publications by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Cyclopropanation Catalyzed by Osmium Porphyrin Complexes Abstract Cyclopropanation of alkenes can be accomplished catalytically2 or stoichiometrically.3 Catalytic systems typically use a diazo reagent as the carbene source and a metal-containing mediator which forms a postulated metal carbene intermediate. Transfer of the carbene fragment from the metal to an alkene produces the cyclopropane product. Despite the wide variety of catalytic cyclopropanation systems, the putative carbene complex has never been isolated or observed in a catalytic system. This is somewhat surprising since the second category of cyclopropanation reactions involves the stoichiometric reaction -
University of California
UC Riverside UC Riverside Electronic Theses and Dissertations Title Towards a Catalytic Asymmetric Cope Rearrangement and the Synthesis and Self-Assembly of Metal-Coordinated Hosts Permalink https://escholarship.org/uc/item/4gc654st Author Moehlig, Melissa Padilla Publication Date 2013 Peer reviewed|Thesis/dissertation eScholarship.org Powered by the California Digital Library University of California UNIVERSITY OF CALIFORNIA RIVERSIDE Towards a Catalytic Asymmetric Cope Rearrangement and the Synthesis and Self- Assembly of Metal-Coordinated Hosts A Dissertation submitted in partial satisfaction of the requirements for the degree of Doctor of Philosophy in Chemistry by Melissa Padilla Moehlig December 2013 Dissertation Committee: Dr. Richard J. Hooley, Chairperson Dr. Catharine H. Larsen Dr. Michael C. Pirrung Copyright by Melissa Padilla Moehlig 2013 The Dissertation of Melissa Padilla Moehlig is approved: Committee Chairperson University of California, Riverside ACKNOWLEDGEMENTS Graduate school has been one of the most rewarding and yet the most exhausting and stressful times of my life. It would not have survived without the help of several people. I would like to thank Dr. Courtney Meyet, Dr. Katherine Djernes, and Yoo-Jin Ghang for their friendship and all the laughs that were necessary to keep me sane. I would like to thank Michael Young, Hou Ung, and Jay-Ar Bendo for our morning coffee breaks, they were crucial to get my day started. I would like to thank Prof. Larsen for teaching me to be independent. I would like to thank Prof. Hooley for all his guidance over the past five years. You are truly a great mentor and I don’t think I would have survived graduate school without your help and advice. -
© Cambridge University Press Cambridge
Cambridge University Press 0521770971 - Modern Methods of Organic Synthesis W. Carruthers and Iain Coldham Index More information Index acidity 1 from alkynes 125–32 acyl anion equivalents 56 from diols 123 acyloin reaction 425 from hydrazones 120 Adams’ catalyst 407 reaction of AD-mix ␣ 352 with carbenes 303–9 AD-mix  352 with dienes in Diels–Alder reaction 162 agelastatin A 376 with radicals 280–98 AIBN 268 reduction of 322, 408–13, 459 alane 437, 444 alkenyllithium species 57, 59 alcohols alkylation 1–19 deoxygenation 270 asymmetric 37 from alkenes 323, 349 with enamines 1, 17 from carbonyl compounds 416, 421, 423, 434–56 with enolates 1–16 oxidation 378–93 with metalloenamines 16 aldehydes alkyl halides alkylation of 17 oxidation to carbonyl compounds 384 as dienophiles in Diels–Alder reaction 169 reductive cleavage to hydrocarbons 269, 406, 442 decarbonylation of 419 alkyllithium species 46 from alcohols 380 alkynes from alkenes 325, 360, 364 conversion to alkenes 125–32, 414 oxidation of 392 deprotonation of 58 reduction of 435, 439, 443 hydrometallation 128 reductive dimerization of 148, 425 preparation of 137 Alder–ene reaction 231 reduction of 125 aldol reaction 27–36 allopumiliotoxin 58 diastereoselective 32 allosamidin disaccharides 272 enantioselective 41 allylic organometallics 71–4 aldosterone 276 allylic oxidation 374 alkenes allylic 1,3-strain 26, 73, 351 allylic oxidation of 374 -allylpalladium complexes 98 conversion to alcohols 323 amabiline 220 conversion to ketones (Wacker reaction) 365 ambruticin S 308 epoxidation -