DOCSLIB.ORG

Palladium-Catalyzed Borylation and Cross-Coupling of Aryl and Heteroaryl Halides Utilizing Dibora Derivatives

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Palladium-Catalyzed Borylation and Cross-Coupling of Aryl and Heteroaryl Halides Utilizing Dibora Derivatives University of Pennsylvania ScholarlyCommons Publicly Accessible Penn Dissertations 2012 Palladium-Catalyzed Borylation And Cross-Coupling Of Aryl And Heteroaryl Halides Utilizing Dibora Derivatives Sarah Little Jane Trice University of Pennsylvania, [email protected] Follow this and additional works at: https://repository.upenn.edu/edissertations Part of the Organic Chemistry Commons Recommended Citation Trice, Sarah Little Jane, "Palladium-Catalyzed Borylation And Cross-Coupling Of Aryl And Heteroaryl Halides Utilizing Dibora Derivatives" (2012). Publicly Accessible Penn Dissertations. 712. https://repository.upenn.edu/edissertations/712 This paper is posted at ScholarlyCommons. https://repository.upenn.edu/edissertations/712 For more information, please contact [email protected]. Palladium-Catalyzed Borylation And Cross-Coupling Of Aryl And Heteroaryl Halides Utilizing Dibora Derivatives Abstract ABSTRACT PALLADIUM-CATALYZED BORYLATION AND CROSS-COUPLING OF ARYL AND HETEROARYL HALIDES UTILIZING DIBORA DERIVATIVES Sarah Little Jane Trice Professor Gary A. Molander Although much current research focuses on developing new boron reagents and identifying robust catalytic systems for the cross-coupling of these reagents, the fundamental preparations of the nucleophilic partners (i.e., boronic acids and derivatives) has been studied to a lesser extent. Most current methods to access boronic acids are indirect and require harsh conditions or expensive reagents. Therefore, we sought to provide a simple, efficient, and direct synthesis of arylboronic acids. Utilizing aryl halides and an underutilized reagent, tetrahydroxydiboron B2(OH)4, we developed a palladium-catalyzed method that now provides access to boronic acids in high yield. The method eliminates the necessity to employ the extremely wasteful and most commonly used source of boron, bis(pinacolato)diboron. The first method developed focused on the borylation of the less expensive and more commercially available aryl chlorides. We demonstrated that most functional groups are well tolerated under the mild reaction conditions, providing the corresponding trifluoroborate in good to excellent yield for most subtrates. We also demonstrated that the crude boronic acid could be easily and efficiently converted to a myriad of boronate esters. The method was later extended to include aryl and heteroaryls bromides, chlorides, and triflates. We went on to demonstrate that we could achieve similar results with the synthetic precursor to B2(OH)4, tetrakis(dimethylamino)diboron. We also demonstrated that we could perform a one-pot, two-step borylation/Suzuki cross-coupling reaction. And Finally, through the use of ethylene glycol as an additive to the borylation reaction with B2(OH)4, we were able to access heteroaryl substrates that were difficulto t obtain in good yield with our optimized methods. Using this strategy, we were able to access one-pot borylation/Suzuki cross-coupled products between two heteroaryls in high yield. Degree Type Dissertation Degree Name Doctor of Philosophy (PhD) Graduate Group Chemistry First Advisor Gary A. Molander Keywords Bis-boronic acid (BBA), Boronic Acid, Palladium Catalysis, Suzuki-Miyaura Cross-Coupling, tetrahydroxydiboron, tetrakis(dimethylamino)diboron Subject Categories Organic Chemistry This dissertation is available at ScholarlyCommons: https://repository.upenn.edu/edissertations/712 PALLADIUM-CATALYZED BORYLATION AND CROSS-COUPLING OF ARYL AND HETEROARYL HALIDES UTILIZING DIBORA DERIVATIVES Sarah Little Jane Trice A DISSERTATION In Chemistry Presented to the Faculties of the University of Pennsylvania in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy 2012 Supervisor of Dissertation Gary A. Molander Professor of Chemistry Department Chair Graduate Group Chairperson Tobias Baumgart, Associate Professor of Chemistry Dissertation Committee Patrick Walsh, Professor of Chemistry Marisa Kozlowski, Professor of Chemistry Donna Huryn, Adjunct Professor of Chemistry PALLADIUM-CATALYZED BORYLATION AND CROSS-COUPLING OF ARYL AND HETEROARYL HALIDES UTILIZING DIBORA DERIVATIVES COPYRIGHT Sarah Little Jane Trice 2012 ii To my Grandmother Margaret, who always told me to “look it up!” iii ACKNOWLEDGEMENTS I would first like to thank my advisor, Dr. Molander, who took a chance on taking me into his lab. His guidance and freedom allowed me to grow into the scientist I have become today and for that I am very grateful. I would also like to thank my committee members, Patrick Walsh, Marisa Kozlowski, and Donna Huryn for their encouragement during my three short years under their care. Each one of them offered invaluable advice that helped guide me through my journey. I would like to thank all of the past and present Molander group members. I learned a lot from each and every one of them. Interestingly, the most important things I took away from my experiences with them had little to do with chemistry and more about people and growing up. I would like to extend a special thank you to Dr. Steven Kennedy for his enthusiasm for SCIENCE! Throughout our time together we accomplished a lot and produced truly beautiful work and for that I am eternally grateful. I would also like to thank Livia Cavalcanti for reminding me to sing and to follow my heart. Dee and Andreea, I thank them for being themselves and never wavering. A special thanks goes to Rosaura Padilla for being a true friend from the beginning to the end. Ro will always be in my fondest memories of graduate school. I had the great pleasure of mentoring an undergraduate student, Melvin Lim in my last year as a graduate student. Melvin taught me how to guide a student through the process of discovery and showed me that the most talented people merely need a gentle iv hand along the way. I would also like to thank Madeleine Jouillé for her kindness and support. I look forward to many more dinners and glasses of wine on her balcony. I am very grateful for the Wharton School and my professors there that offered me a new perspective on the world and my place in it. My time spent in the classes at Wharton will become an essential piece to my success as I re-enter the business world at Merck. I would also like to thank the members of my Wharton Crew. The many miles on the river taught me about teamwork, dedication, and how to have fun and work hard at the same time. I would not have been able to accomplish my doctoral degree without the support of Dr. Joseph Vacca. His belief in my talent and drive are what allowed me to pursue my dream of graduate school. I will never forget his kindness and guidance. I would also like to thank all of the past and present members of Merck Medicinal Chemistry, especially Pablo DeLeon for his constant cheering from the sidelines and for showcasing my methods to the department. He is truly an innovator. Finally, I would like to thank my family, whose unwavering support helped me to stay on the path to follow my dreams. I would like to especially thank my grandparents for their love of learning. They instilled in me the desire to always find the answer and to never stop learning. I thank my mother for taking my education seriously and for teaching me take care of myself. Her sacrifices and constant support helped make me into the strong and confident woman I am today. Lastly, I would like to thank Jourdan. Without his love and support I may not have made it through this. v ABSTRACT PALLADIUM-CATALYZED BORYLATION AND CROSS-COUPLING OF ARYL AND HETEROARYL HALIDES UTILIZING DIBORA DERIVATIVES Sarah Little Jane Trice Professor Gary A. Molander Although much current research focuses on developing new boron reagents and identifying robust catalytic systems for the cross-coupling of these reagents, the fundamental preparations of the nucleophilic partners (i.e., boronic acids and derivatives) has been studied to a lesser extent. Most current methods to access boronic acids are indirect and require harsh conditions or expensive reagents. Therefore, we sought to provide a simple, efficient, and direct synthesis of arylboronic acids. Utilizing aryl halides and an underutilized reagent, tetrahydroxydiboron B2(OH)4, we developed a palladium-catalyzed method that now provides access to boronic acids in high yield. The method eliminates the necessity to employ the extremely wasteful and most commonly used source of boron, bis(pinacolato)diboron. The first method developed focused on the borylation of the less expensive and more commercially available aryl chlorides. We demonstrated that most functional vi groups are well tolerated under the mild reaction conditions, providing the corresponding trifluoroborate in good to excellent yield for most subtrates. We also demonstrated that the crude boronic acid could be easily and efficiently converted to a myriad of boronate esters. The method was later extended to include aryl and heteroaryls bromides, chlorides, and triflates. BF3K KHF2 HO OH B B OH X HO OH B OH Pd(0) H O OH X = Cl, Br, I, OTf O B O We went on to demonstrate that we could achieve similar results with the synthetic precursor to B2(OH)4, tetrakis(dimethylamino)diboron. N X N N BF K Pd(0) B KHF2 3 + B B N N N We also demonstrated that we could perform a one-pot, two-step borylation/Suzuki cross-coupling reaction. HO OH B B OH aryl or X HO OH B heteroaryl halide OH Pd(0) X = Cl, Br vii And Finally, through the use of ethylene glycol as an additive to the borylation reaction with B2(OH)4, we were able to access heteroaryl substrates that were
Load more

Recommended publications
  • Aldrich FT-IR Collection Edition I Library
    Aldrich FT-IR Collection Edition I Library Library Listing – 10,505 spectra This library is the original FT-IR spectral collection from Aldrich. It includes a wide variety of pure chemical compounds found in the Aldrich Handbook of Fine Chemicals. The Aldrich Collection of FT-IR Spectra Edition I library contains spectra of 10,505 pure compounds and is a subset of the Aldrich Collection of FT-IR Spectra Edition II library. All spectra were acquired by Sigma-Aldrich Co. and were processed by Thermo Fisher Scientific. Eight smaller Aldrich Material Specific Sub-Libraries are also available. Aldrich FT-IR Collection Edition I Index Compound Name Index Compound Name 3515 ((1R)-(ENDO,ANTI))-(+)-3- 928 (+)-LIMONENE OXIDE, 97%, BROMOCAMPHOR-8- SULFONIC MIXTURE OF CIS AND TRANS ACID, AMMONIUM SALT 209 (+)-LONGIFOLENE, 98+% 1708 ((1R)-ENDO)-(+)-3- 2283 (+)-MURAMIC ACID HYDRATE, BROMOCAMPHOR, 98% 98% 3516 ((1S)-(ENDO,ANTI))-(-)-3- 2966 (+)-N,N'- BROMOCAMPHOR-8- SULFONIC DIALLYLTARTARDIAMIDE, 99+% ACID, AMMONIUM SALT 2976 (+)-N-ACETYLMURAMIC ACID, 644 ((1S)-ENDO)-(-)-BORNEOL, 99% 97% 9587 (+)-11ALPHA-HYDROXY-17ALPHA- 965 (+)-NOE-LACTOL DIMER, 99+% METHYLTESTOSTERONE 5127 (+)-P-BROMOTETRAMISOLE 9590 (+)-11ALPHA- OXALATE, 99% HYDROXYPROGESTERONE, 95% 661 (+)-P-MENTH-1-EN-9-OL, 97%, 9588 (+)-17-METHYLTESTOSTERONE, MIXTURE OF ISOMERS 99% 730 (+)-PERSEITOL 8681 (+)-2'-DEOXYURIDINE, 99+% 7913 (+)-PILOCARPINE 7591 (+)-2,3-O-ISOPROPYLIDENE-2,3- HYDROCHLORIDE, 99% DIHYDROXY- 1,4- 5844 (+)-RUTIN HYDRATE, 95% BIS(DIPHENYLPHOSPHINO)BUT 9571 (+)-STIGMASTANOL
    [Show full text]
  • Pd/C-Catalyzed Suzuki Cross- and Self- Couplings &
    PD/C-CATALYZED SUZUKI CROSS- AND SELF- COUPLINGS & THE DEVELOPMENT OF A LAB-SCALE HYDROGENATION SYSTEM by JENG-SHIOU CHEN A Dissertation submitted to the Graduate School-New Brunswick Rutgers, The State University of New Jersey In partial fulfillment of the requirements For the degree of Doctor of Philosophy Graduate Program in Chemical and Biochemical Engineering Written under the direction of Professor Johannes G. Khinast And approved by ________________________ ________________________ ________________________ ________________________ New Brunswick, New Jersey Jan. 2008 ABSTRACT OF THE DISSERTATION PD/C-CATALYZED SUZUKI CROSS- AND SELF- COUPLINGS & THE DEVELOPMENT OF A LAB-SCALE HYDROGENATION SYSTEM By JENG-SHIOU CHEN Dissertation Directors: Professor Johannes G. Khinast Suzuki couplings have become an efficient and clean strategy for the preparation of biologically active functionalized biphenyls, which are important building blocks for pharmaceutical and agricultural compounds. Among all catalysts of choice for Suzuki couplings, palladium on carbon (Pd/C) is most frequently used for industrial applications due to its high catalytic activity, low cost and easy removal from the reaction mixture. Using a model coupling reaction of biphenylacetic acid, we intended to provide a thorough understanding of Pd/C-catalyzed Suzuki couplings for a straightforward industrial implementation. A detailed investigation of the reaction parameters was carried out in Chapter 2. The experimental observations indicate that excess amount of the borate is helpful to accelerate the reaction and 2 moles eq. of a strong base is the best choice for the reaction. Furthermore, our results suggest that transmetalation is the rate-limiting step of the Pd/C-catalyzed Suzuki couplings and also show that [OH-] is a critical factor affecting the reaction rate.
    [Show full text]
  • The Development and Application of Metal-Catalyzed Processes for Organic Synthesis
    The Development and Application of Metal-Catalyzed Processes for Organic Synthesis by Edward J. Hennessy B.A. Chemistry Northwestern University, 2000 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 2005 © 2005 Massachusetts Institute of Technology All Rights Reserved Signature of Author: " - - 1_"' .Da-uirnt of Chemistry May 19, 2005 Certified by: Stephen L. Buchwald Camille Dreyfus Professor of Chemistry Thesis Supervisor Accepted by: Robert W. Field Chairman, Departmental Committee on Graduate Students ARCHIVES: This doctoral thesis has been examined by a committee of the Department of Chemistry as follows: -/ Professor Gregory C. Fu: " Ch Chair Professor Stephen L. Buchwald Thesis Supervisor Professor Timothy M. Swager: , -L i \ O 2 The Development and Application of Metal-Catalyzed Processes for Organic Synthesis by Edward J. Hennessy Submitted to the Department of Chemistry on May 19, 2005 in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy at the Massachusetts Institute of Technology ABSTRACT Chapter 1. Copper-Catalyzed Arylation of Stabilized Carbanions A mild, general catalytic system for the synthesis of a-aryl malonates has been developed. Aryl iodides bearing a variety of functional groups can be effectively coupled to diethyl malonate in high yields using inexpensive and widely available reagents, making this a superior method to those previously described that employ copper reagents or catalysts. The functional group tolerance of the process developed makes it complementary to analogous palladium-catalyzed couplings. Importantly, a set of mild reaction conditions has been developed that minimize product decomposition, a problem that had not been addressed previously in the literature.
    [Show full text]
  • Frontiers in Iridium-Catalyzed CH Borylation
    Frontiers in Iridium-Catalyzed C-H Borylation: Attaining Novel Reactivity and Selectivity By Matthew Alan Larsen A dissertation submitted in partial satisfaction of the requirements for the degree of Doctor of Philosophy in Chemistry in the Graduate Division of the University of California, Berkeley Committee in charge: Professor John F. Hartwig, Chair Professor Robert G. Bergman Professor Alexis T. Bell Fall 2016 Abstract Frontiers in Iridium-Catalyzed C-H Borylation: Attaining Novel Reactivity and Selectivity By Matthew Alan Larsen Doctor of Philosophy in Chemistry University of California, Berkeley Professor John F. Hartwig, Chair The following dissertation discusses the development of novel methodology for the catalytic borylation of C-H bonds and includes in-depth studies on the mechanism and selectivity of these synthetic transformations. These methods include the borylation of heteroaryl C-H bonds, the selective borylation of benzylic C-H bonds, and the directed and undirected borylation of unactivated alkyl C-H bonds. Chapter 1 contains a comprehensive review of C-H borylation methodology. This review focuses on the initial development of catalytic C-H borylation and on the state-of- the-art of methodology for the undirected and directed borylation of aryl, benzylic, and alkyl C-H bonds. Additionally, this review highlights knowledge gaps and unsolved challenges. Furthermore, this review provides the author’s opinion on future directions for research on the borylation of C-H bonds. Chapter 2 describes the study of the iridium-catalyzed borylation of heteroaryl C- H bonds. Contained is an examination of the scope of the borylation of heterocycles containing more than one heteroatom and rules for predicting the site-selectivity of this reaction.
    [Show full text]
  • Nucleophilic Aromatic Substitution
    NUCLEOPHILIC AROMATIC SUBSTITUTION Ms. Prerana Sanas M.Pharm (Pharmceutical Chemistry) Asst.Professor, NCRD’s Sterling Institute of Pharmacy Nerul Navi Mumbai Nucleophilic aromatic substitution results in the substitution of a halogen X on a benzene ring by a nucleophile (:Nu– ). Aryl halides undergo a limited number of substitution reactions with strong nucleophiles. NAS occurs by two mechanisms i) Bimoleccular displacement (Addition –Elimination) ii) Benzyne Formation( Elimination –Addition) 7/5/2019 Ms.Prerana Sanas 2 Bimolecular displacement (Addition – Elimination) Aryl halides with strong electron-withdrawing groups (such as NO2) on the ortho or para positions react with nucleophiles to afford substitution products. For example, treatment of p-chloronitrobenzene with hydroxide (– OH) affords p-nitrophenol by replacement of Cl by OH. Nucleophilic aromatic substitution occurs with a variety of strong nucleophiles, including – OH, – OR, – NH2, – SR, and in some cases, neutral nucleophiles such as NH3 and RNH2 . 7/5/2019 Ms.Prerana Sanas 3 Mechanism…… The mechanism of these reactions has two steps: Step i) Addition of the nucleophile (:Nu– ) forms a resonance-stabilized carbanion with a new C – Nu bond—three resonance structures can be drawn. • Step [1] is rate-determining since the aromaticity of the benzene ring is lost. In Step ii) loss of the leaving group re-forms the aromatic ring. This step is fast because the aromaticity of the benzene ring is restored. 7/5/2019 Ms.Prerana Sanas 4 Factors affecting Bimolecular displacement Increasing the number of electron-withdrawing groups increases the reactivity of the aryl halide. Electron-withdrawing groups stabilize the intermediate carbanion, and by the Hammond postulate, lower the energy of the transition state that forms it.
    [Show full text]
  • The Total Synthesis of Securinine and Other Methodology Studies
    University of Windsor Scholarship at UWindsor Electronic Theses and Dissertations Theses, Dissertations, and Major Papers 2010 The total synthesis of securinine and other methodology studies Bhartesh Dhudshia University of Windsor Follow this and additional works at: https://scholar.uwindsor.ca/etd Recommended Citation Dhudshia, Bhartesh, "The total synthesis of securinine and other methodology studies" (2010). Electronic Theses and Dissertations. 8275. https://scholar.uwindsor.ca/etd/8275 This online database contains the full-text of PhD dissertations and Masters’ theses of University of Windsor students from 1954 forward. These documents are made available for personal study and research purposes only, in accordance with the Canadian Copyright Act and the Creative Commons license—CC BY-NC-ND (Attribution, Non-Commercial, No Derivative Works). Under this license, works must always be attributed to the copyright holder (original author), cannot be used for any commercial purposes, and may not be altered. Any other use would require the permission of the copyright holder. Students may inquire about withdrawing their dissertation and/or thesis from this database. For additional inquiries, please contact the repository administrator via email ([email protected]) or by telephone at 519-253-3000ext. 3208. The Total Synthesis of Securinine and Other Methodology Studies by Bhartesh Dhudshia A Dissertation Submitted to the Faculty of Graduate Studies through the Department of Chemistry and Biochemistry in Partial Fulfillment of the Requirements
    [Show full text]
  • 1 Structure, Properties, and Preparation of Boronic Acid Derivatives Overview of Their Reactions and Applications Dennis G
    j1 1 Structure, Properties, and Preparation of Boronic Acid Derivatives Overview of Their Reactions and Applications Dennis G. Hall 1.1 Introduction and Historical Background Structurally, boronic acids are trivalent boron-containing organic compounds that possess one carbon-based substituent (i.e., a CÀB bond) and two hydroxyl groups to fill the remaining valences on the boron atom (Figure 1.1). With only six valence electrons and a consequent deficiency of two electrons, the sp2-hybridized boron atom possesses a vacant p-orbital. This low-energy orbital is orthogonal to the three substituents, which are oriented in a trigonal planar geometry. Unlike carbox- ylic acids, their carbon analogues, boronic acids, are not found in nature. These abiotic compounds are derived synthetically from primary sources of boron such as boric acid, which is made by the acidification of borax with carbon dioxide. Borate esters, one of the key precursors of boronic acid derivatives, are made by simple dehydration of boric acid with alcohols. The first preparation and isolation of a boronic acid was reported by Frankland in 1860 [1]. By treating diethylzinc with triethylborate, the highly air-sensitive triethylborane was obtained, and its slow oxidation in ambient air eventually provided ethylboronic acid. Boronic acids are the products of a twofold oxidation of boranes. Their stability to atmospheric oxidation is considerably superior to that of borinic acids, which result from the first oxidation of boranes. The product of a third oxidation of boranes, boric acid, is a very stable and relatively benign compound to humans (Section 1.2.2.3). Their unique properties and reactivity as mild organic Lewis acids, coupled with their stability and ease of handling, are what make boronic acids a particularly attractive class of synthetic intermediates.
    [Show full text]
  • Organic Synthesis: New Vistas in the Brazilian Landscape
    Anais da Academia Brasileira de Ciências (2018) 90(1 Suppl. 1): 895-941 (Annals of the Brazilian Academy of Sciences) Printed version ISSN 0001-3765 / Online version ISSN 1678-2690 http://dx.doi.org/10.1590/0001-3765201820170564 www.scielo.br/aabc | www.fb.com/aabcjournal Organic Synthesis: New Vistas in the Brazilian Landscape RONALDO A. PILLI and FRANCISCO F. DE ASSIS Instituto de Química, UNICAMP, Rua José de Castro, s/n, 13083-970 Campinas, SP, Brazil Manuscript received on September 11, 2017; accepted for publication on December 29, 2017 ABSTRACT In this overview, we present our analysis of the future of organic synthesis in Brazil, a highly innovative and strategic area of research which underpins our social and economical progress. Several different topics (automation, catalysis, green chemistry, scalability, methodological studies and total syntheses) were considered to hold promise for the future advance of chemical sciences in Brazil. In order to put it in perspective, contributions from Brazilian laboratories were selected by the citations received and importance for the field and were benchmarked against some of the most important results disclosed by authors worldwide. The picture that emerged reveals a thriving area of research, with new generations of well-trained and productive chemists engaged particularly in the areas of green chemistry and catalysis. In order to fulfill the promise of delivering more efficient and sustainable processes, an integration of the academic and industrial research agendas is to be expected. On the other hand, academic research in automation of chemical processes, a well established topic of investigation in industrial settings, has just recently began in Brazil and more academic laboratories are lining up to contribute.
    [Show full text]
  • Durham E-Theses
    Durham E-Theses Functionalised Pyridyl- and Pyrimidyl- Boronic acids and derived new Biheteroaryls Smith, Amy Elizabeth How to cite: Smith, Amy Elizabeth (2005) Functionalised Pyridyl- and Pyrimidyl- Boronic acids and derived new Biheteroaryls, Durham theses, Durham University. Available at Durham E-Theses Online: http://etheses.dur.ac.uk/2751/ Use policy The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that: • a full bibliographic reference is made to the original source • a link is made to the metadata record in Durham E-Theses • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders. Please consult the full Durham E-Theses policy for further details. Academic Support Oce, Durham University, University Oce, Old Elvet, Durham DH1 3HP e-mail: [email protected] Tel: +44 0191 334 6107 http://etheses.dur.ac.uk 2 University of Durham A Thesis Entitled Functionalised Pyridyl- and Pyrimidyl- Boronic Acids and Derived New Biheteroaryls Submitted by Amy Elizabeth Smith, B.Sc. (Hons) (Ustinov College) Department of Chemistry A Candidate for the Degree of Doctor of Philosophy 2005 The copyright of this thesis rests wnh the author or the university to which к was submitted. No quotation from It, or Information derived from It may be published wHhout the prior written consent of the author or university, and any Information derived from ท should be acknowledged.
    [Show full text]
  • 2D Porous Polymers with Sp2-Carbon Connections
    2D Porous Polymers with sp2-Carbon Connections and Sole sp2-Carbon Skeletons Jialing Kang, Senhe Huang, Kaiyue Jiang, Chenbao Lu, Zhenying Chen, Jinhui Zhu, Chongqing Yang, Artur Ciesielski, Feng Qiu, Xiaodong Zhuang To cite this version: Jialing Kang, Senhe Huang, Kaiyue Jiang, Chenbao Lu, Zhenying Chen, et al.. 2D Porous Polymers with sp2-Carbon Connections and Sole sp2-Carbon Skeletons. Advanced Functional Materials, Wiley, 2020, 30 (27), pp.2000857. 10.1002/adfm.202000857. hal-03117175 HAL Id: hal-03117175 https://hal.archives-ouvertes.fr/hal-03117175 Submitted on 20 Jan 2021 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. Two-Dimensional Porous Polymers with sp2-Carbon Connections and Sole sp2-Carbon Skeletons Jialing Kang, Senhe Huang, Kaiyue Jiang, Chenbao Lu, Zhenying Chen, Jinhui Zhu, Chongqing Yang,* Artur Ciesielski, Feng Qiu,* and Xiaodong Zhuang* J. Kang, S. Huang, K. Jiang, C. Lu, Z. Chen, Dr. J. Zhu, Dr. C. Yang, Prof. X. Zhuang The Meso-Entropy Matter Lab, SChool of Chemistry and ChemiCal Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China E-mail: [email protected], [email protected] J. Kang, Prof.
    [Show full text]
  • Desperately Seeking for the Catalytic Species in Suzuki-Miyaura Reaction Amine Bourouina
    Desperately Seeking For The Catalytic Species In Suzuki-Miyaura Reaction Amine Bourouina To cite this version: Amine Bourouina. Desperately Seeking For The Catalytic Species In Suzuki-Miyaura Reaction. Chemical and Process Engineering. Université de Lyon, 2019. English. NNT : 2019LYSE1258. tel-02482607 HAL Id: tel-02482607 https://tel.archives-ouvertes.fr/tel-02482607 Submitted on 18 Feb 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. N°d’ordre NNT : 2019LYSE1258 THESE de DOCTORAT DE L’UNIVERSITE DE LYON opérée au sein de l’Université Claude Bernard Lyon 1 Ecole Doctorale ED206 Ecole Doctorale de Chimie de Lyon Spécialité de doctorat : Discipline : Procédés Soutenue publiquement le 28/11/2019, par : Amine BOUROUINA Desperately Seeking For The Catalytic Species In Suzuki-Miyaura Reaction Devant le jury composé de : FERRIGNO Rosaria, Professeure des Universités, Université Lyon Présidente HII King Kuok (Mimi), Professeure, L'Imperial College de Londres Rapporteuse RIANT Olivier, Professeur ordinaire, Université Catholique de Louvain Rapporteur
    [Show full text]
  • Reductive Α-Borylation of Α,Β-Unsaturated Esters Using NHC
    Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue Reductive a-borylation of a,b-unsaturated esters using NHC–BH3 activated by I2 as a metal-free Cite this: Chem. Sci.,2019,10,1434 a † All publication charges for this article route to -boryl esters have been paid for by the Royal Society of Chemistry James E. Radcliffe, Valerio Fasano, Ralph W. Adams, Peiran You and Michael J. Ingleson * Useful a-boryl esters can be synthesized in one step from a,b-unsaturated esters using just a simple to access NHC–BH3 (NHC ¼ N-heterocyclic carbene) and catalytic I2. The scope of this reductive a-borylation methodology is excellent and includes a range of alkyl, aryl substituted and cyclic and acyclic a,b-unsaturated esters. Mechanistic studies involving reductive borylation of a cyclic a,b-unsaturated ester with NHC–BD3/I2 indicated that concerted hydroboration of the alkene moiety in the a,b-unsaturated ester proceeds instead of a stepwise process involving initial 1,4-hydroboration; this is in contrast to the recently reported reductive a-silylation. The BH2(NHC) unit can be transformed into Creative Commons Attribution 3.0 Unported Licence. electrophilic BX2(NHC) moieties (X ¼ halide) and the ester moiety can be reduced to the alcohol with the borane unit remaining intact to form b-boryl alcohols. The use of a chiral auxiliary, 8-phenylmenthyl Received 27th September 2018 ester, also enables effective stereo-control of the newly formed C–B bond. Combined two Accepted 17th November 2018 step ester reduction/borane oxidation forms diols, including excellent e.e.
    [Show full text]