DOCSLIB.ORG

And Bis(Germylene) Pincer Type Ligands in Catalysis

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
And Bis(Germylene) Pincer Type Ligands in Catalysis Introducing Bis(silylene) and Bis(germylene) Pincer Type Ligands in Catalysis vorgelegt von M. Sc. Chemie Daniel Gallego Mahecha aus Bogotá D. C., Kolumbien Von der Fakultät II – Mathematik und Naturwissenschaften der Technischen Universität Berlin Institut für Chemie zur Erlangung des akademischen Grades Doktor der Naturwissenschaften - Dr. rer. nat. - genehmigte Dissertation Promotionsausschuss: Vorsitzender: Prof. Dr. Martin Kaupp (TU Berlin) 1. Gutachter: Prof. Dr. Matthias Driess (TU Berlin) 2. Gutachter: Prof. Dr. Thomas Braun (HU Berlin) Tag der wissenschaftlichen Aussprache: 21-04-2015 Berlin 2015 D83 ii DISSERTATION Introducing Bis(silylene) and Bis(germylene) Pincer Type Ligands in Catalysis by M. Sc. Chemistry Daniel Gallego Mahecha from Bogotá D. C., Colombia iii iv Erklärung Die vorliegende Arbeit entstand in der Zeit von Sep. 2011 bis Mar. 2015 unter der Betreuung von Prof. Dr. Matthias Driess am Institut für Chemie der Technischen Universität Berlin. Von Herzen kommend gilt mein Dank meinem verehrten Lehrer Herrn Professor Dr. Matthias Drieß für die Aufnahme in seinen Arbeitskreis, für seine engagierte Unterstützung, und für die Forschungsfreiheit. v vi To my family, Maria del Mar, Diego, Ariel y Nima, Che, Má y Pá, for being always there despite the distance. “Erfahren, was ist es, ernst genommen zu werden und über das andere zu lachen” “Learn what is to be taken seriously and laugh at the rest” Hermann Hesse “Grau, teurer Freund, ist alle Theorie Und grün des Lebens goldner Baum” “Grey, dear friend, is all theory And green the golden tree of life” Faust I – Mephistopheles Goethe “The beauty of a living thing is not the atoms that go into it, but the way those atoms are put together” Cosmos Carl Sagan vii viii Acknowledgements At the beginning of this PhD, the way looked very long and with plenty of unknown and some scary difficulties. However, thanks to the help of many people this journey has been amenable and enjoyable. First, I would like to thank my supervisor Prof. Dr. Matthias Driess who gave me the possibility to work in this very interesting and challenging project independently. It has been very satisfying to learn about main group and organometallic chemistry under his supervision, I am in debt for his commitment in this field. Secondly, I would like to thank Prof. Dr. Thomas Braun for accepting reviewing this dissertation and be part of the jury committee. I would also want to thank the collaboration partners who have been very important for the successful achievements of my scientific research. I thank Prof. Dr. John F. Hartwig at University of California, Berkeley, who through the Einstein Foundation Fellowship worked during the projects of Iridium and Nickel pincer complexes; for his insightful discussions about catalysis and mechanistic studies, and his commitment in chemistry in general. Also I thank Dr. Andreas Brück who took part as the “catalytic partner” in these two projects from Hartwig’s group, Dankeschön. I feel very thankful with the people who helped for the theoretical calculations for a better and complete understanding of the experiments. I thank Prof. Dr. Martin Kaupp and his co-worker Mr. Florian Meier for their passionate, careful and detailed work about the reaction intermediate of the Sonogashira cross-coupling reaction, Dankeschön. Also I thank Prof. Dr. Shigeyoshi Inoue for his contribution on the calculation of the electronic structure of the iron(0) complexes and for his friendship along this PhD, Arigatou gozaimasu Shige Sensei! And Dr. Tibor Szilvási at the University of Budapest, who appeared just at the right time for calculating the key intermediate of the hydrosilylation of ketones; I am happy that at the end the match theory vs. experiment finalized in a draw, köszönöm szépen Tibi! Finally, I feel gratified with the collaboration with Prof. Dr. Martin Oestreich and his co-worker Toni T. Metsänen during the understanding of the catalytic mechanism of the hydrosilylation of ketones. It was great to see the successful organic-inorganic fusion for a deep understanding in the unexpected mechanism for this system, Dankeschön and Kiitos! ix I am strongly in debt with the people who in one or other way always stayed open for a scientific discussion, suggestion or just to give constant support during the tough days. First, I would like to thank my partner and bro’ Gengwen Tan, it has been really incredible to work with such a passionate and bright chemist. Man, thanks to you this journey was more than simple research but a travel to wonderful and deep understanding of our crazy reactions day by day. I learnt a lot from you not only from chemistry but life as well, Xièxiè wǒ de péngyǒu! I also thank Dr. Burgert Blom, mostly known as Dr. UNO, who became a constant support and a really important guide during my scientific research. Man, I am thoroughly in debt with you for your careful revision of this dissertation. It has been a pleasure to work to your side with our little paws and to laugh as well, despite the stressful moments, Thanks a lot UNO! I am in debt with my mentor at the beginning of my PhD Dr. Wenyuan Wang, who with his patience I got to know the difficulties during this type of chemistry. Also, he taught me that science is an universal language and even when we could not understand each other quite well either in English, German, Chinese, or Spanish, at the end the chemistry knowledge could be transferred without any inconvenient, Xièxiè! My office partners deserve also big thanks because of their constant support, discussions and relaxing chats during the working days. Arindam and Prashant, you both are great, still I have to learn more about Indian cousine and its special and spiiiiiiicy taste! I would also like to thank Nils, who has been a very important friend and support during the last year of the PhD, vielen Dank für deine Unterstützenden Worte mein Freund! Also I am thoroughly in debt with Dr. Stephan Enthaler for his scientific discussions, suggestions and revision of this dissertation, Dankeschön! I also thank all the group members of Metalorganics and Inorganic Materials group under the supervision of Prof. Dr. Matthias Driess, and the groups of Dr. Stephan Enthaler and Prof. Dr. Shigeyoshi Inoue, for their daily support. I especially thank the secretary Andrea Rahmel for all the help in the bureaucratic work during my PhD, Vielen Dank! I also thank all technicians from the Institute für Chemie at the Technische Universität Berlin for their constant help and work. Especially, I would like to thank Paula Nidorf and Dr. Elisabeth Irran for the measuring of single crystals and solving the disordering of the XRD crystallographic structures. Mrs. Christine Klose and Dr. Maria Schlangen for their help x during the mass spectra acquisition of the sensitive metal complexes. And, Samantha Voges and Dr. Jan Dirk Epping for their help during the NMR spectra acquisition. I am thoroughly thankful with the Cluster in Catalysis UniCat in Berlin for giving me the scholarship during my PhD studies. It has been a pleasure to work in such interdisciplinary environment learning from the different fields of catalysis. Also, I thank the graduate school BIG-NSE, in which I took part as fellow, especially to Dr. Jean-Philippe Lonjaret for coordinating the different activities and act as a catalyst for the social meetings with the BIG-NSE students. I thank all my BIG-NSE batch mates who became part of my family in Berlin. Meine liebe crazy Fanni, thanks for all your happiness and football matches either as spectator or player, I am your fan # 1! Mopsi I will always remember your monstrous speed of drinking beer and your flirting skills after the 6th one hahaha. Paddy my rock star and party man, I enjoyed a lot each of your gigs and hic(s)…cops hehehe. Meine liebe katze Laura, happiness and craziness is a perfect mix to being just you, you became like my dear German sister Miaaauuu! Seti, your passion and courage are an inspiration to demand the rights for people for a better world, thanks for keeping this flame alive. Linyu, you and your Chinese wine will always produce me a headache but a nice remembrance of a passionate and involved chemist, Gānbēi! Xunhua, your commitment is an example to follow for a successful career. Matthias, man thanks for showing that theoreticians are not always at the PC but can have an enjoyable way of seeing life. And my shy a pretty Nhan, I really wish to had share more with you but unfortunately chemistry made you disappear, hope you will keep doing great! Also all the other people from different batches, especially the latin mafia Lauris, Maria, Javier, and Ines, it was always nice to have a moment for Spanish refreshment out of all the other languages, gracias ;) This thesis would not have been successful with all the support from the people who always were sending the best energy from the distance. All my university colleagues from the Universidad Nacional de Colombia with their constant support made me possible to represent them with all my best. Especially to Lina, Ingrid, Julio Cesar, Patron, Mikel with their supporting words during the tough times. And my brother and partner Edwin with his humble character of seeing chemistry as a hobby and enjoying every single second of life. xi Pelao, you taught me to be serious at work and laugh at the rest; to be generous with everyone who needs it and being there supporting other ones, even when you are not in the best situation. Hermano, I hope that our dream to create a collaborative research group in organometallic chemistry and homogeneous catalysis, one day will become for real, starting a new wave of research in our adorable country Colombia! I thank deeply from my heart to Andrea, my girlfriend, for being the star in the darkness; for being the balance we all need in love; for her constant support and trust on my capacity not just as chemist but as human being.
Load more

Recommended publications
  • Silylation and Characterization of of Piroxicam with Some Silylating Reagents
    Silylation and characterization of of piroxicam with some silylating reagents Mohammad Galehassadi ( [email protected] ) Azarbaijan Shahid Madani University Somayeh Jodeiri Azarbaijan Shahid Madani University Research Article Keywords: Piroxicam, Silyl ether, Organosilicon, Drug delivery, Lipophilic Posted Date: March 22nd, 2021 DOI: https://doi.org/10.21203/rs.3.rs-345479/v1 License: This work is licensed under a Creative Commons Attribution 4.0 International License. Read Full License Silylation and characterization of of piroxicam with some silylating reagents Mohammad. galehassadi, *, a Somayeh Jodeiri a Department of Chemistry, Azarbaijan Shahid Madani University, Tabriz, Iran; e-mail: Email:[email protected] Tel: +984134327541 Mobile: +989144055400 Abstract: In this work, we synthesized some organosilicon derivatives of piroxicam. Due to the some properties of organosilicon compounds, including increased lipophilicity and thermal stabilization and prodrug for drugs, some silyl ethers of this drug were synthesized and characterized..Increasing of the lipophilic properties of this drug can be very important in the rate of absorption and its effectiveness. Graphic abstract: Keywords: Piroxicam, Silyl ether, Organosilicon, Drug delivery, Lipophilic 1.Introduction: Piroxicam is a painkiller and its main use is to reduce or stop pain. In osteoarthritis, this drug has anti-inflammatory effects. This drug is used to treat many diseases such as headache and toothache, leg pain and piroxicam reduces the production of prostaglandins by controlling cyclooxygenase, thus showing its effectiveness in reducing and eliminating pain. It is also used to relieve joint, bone and muscle pain. It is even used to control gout and menstrual cramps. It binds to a large amount of protein and is metabolized in the liver and then excreted in the urine.
    [Show full text]
  • Silyl Ketone Chemistry. Preparation and Reactions of Silyl Allenol Ethers. Diels-Alder Reactions of Siloxy Vinylallenes Leading to Sesquiterpenes2
    J. Am. Chem. SOC.1986, 108, 7791-7800 7791 pyrany1oxy)dodecanoic acid, 1.38 1 g (3.15 mmol) of GPC-CdCIz, 0.854 product mixture was then filtered and concentrated under reduced g (7.0 mmol) of 4-(dimethylamino)pyridine, and 1.648 g (8.0 mmol) of pressure. The residue was dissolved in 5 mL of solvent B and passed dicyclohexylcarbodiimide was suspended in 15 mL of dry dichloro- through a 1.2 X 1.5 cm AG MP-50 cation-exchange column in order to methane and stirred under nitrogen in the dark for 40 h. After removal remove 4-(dimethylamino)pyridine. The filtrate was concentrated under of solvent in vacuo, the residue was dissolved in 50 mL of CH30H/H20 reduced pressure, dissolved in a minimum volume of absolute ethanol, (95/5, v/v) and stirred in the presence of 8.0 g of AG MP-50 (23 OC, and then concentrated again. Chromatographic purification of the res- 2 h) to allow for complete deprotection of the hydroxyl groups (monitored idue on a silica gel column (0.9 X 6 cm), eluting first with solvent A and by thin-layer chromatography)." The resin was then removed by fil- then with solvent C (compound 1 elutes on silica as a single yellow band), tration and the solution concentrated under reduced pressure. The crude afforded, after drying [IO h, 22 OC (0.05 mm)], 0.055 g (90%) of 1 as product (2.75 g). obtained after drying [12 h, 23 OC (0.05 mm)], was a yellow solid: R 0.45 (solvent C); IR (KBr) ucz0 1732, uN(cH3)3 970, then subjected to chromatographic purification by using a 30-g (4 X 4 1050, 1090cm-'; I' H NMR (CDCI,) 6 1.25 (s 28 H, CH2), 1.40-2.05 (m, cm) silica gel column, eluting with solvents A and C, to yield 0.990 g 20 H, lipoic-CH,, CH2CH20,CH2CH,C02), 2.3 (t.
    [Show full text]
  • Activation of Silicon Bonds by Fluoride Ion in the Organic Synthesis in the New Millennium: a Review
    Activation of Silicon Bonds by Fluoride Ion in the Organic Synthesis in the New Millennium: A Review Edgars Abele Latvian Institute of Organic Synthesis, 21 Aizkraukles Street, Riga LV-1006, Latvia E-mail: [email protected] ABSTRACT Recent advances in the fluoride ion mediated reactions of Si-Η, Si-C, Si-O, Si-N, Si-P bonds containing silanes are described. Application of silicon bonds activation by fluoride ion in the syntheses of different types of organic compounds is discussed. A new mechanism, based on quantum chemical calculations, is presented. The literature data published from January 2001 to December 2004 are included in this review. CONTENTS Page 1. INTRODUCTION 45 2. HYDROSILANES 46 3. Si-C BOND 49 3.1. Vinyl and Allyl Silanes 49 3.2. Aryl Silanes 52 3.3. Subsituted Alkylsilanes 54 3.4. Fluoroalkyl Silanes 56 3.5. Other Silanes Containing Si-C Bond 58 4. Si-N BOND 58 5. Si-O BOND 60 6. Si-P BOND 66 7. CONCLUSIONS 66 8. REFERENCES 67 1. INTRODUCTION Reactions of organosilicon compounds catalyzed by nucleophiles have been under extensive study for more than twenty-five years. In this field two excellent reviews were published 11,21. Recently a monograph dedicated to hypervalent organosilicon compounds was also published /3/. There are also two reviews on 45 Vol. 28, No. 2, 2005 Activation of Silicon Bonds by Fluoride Ion in the Organic Synthesis in the New Millenium: A Review fluoride mediated reactions of fluorinated silanes /4/. Two recent reviews are dedicated to fluoride ion activation of silicon bonds in the presence of transition metal catalysts 151.
    [Show full text]
  • The Synthesis of N-Substituted Ferrocenes and C–H Activation
    View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Publikationsserver der RWTH Aachen University The Synthesis of N -Substituted Ferrocenes and C–H Activation Towards the Synthesis of Organosilanols Salih Oz¸cubuk¸cu¨ Dissertation The Synthesis of N -Substituted Ferrocenes and C–H Activation Towards the Synthesis of Organosilanols Von der Fakult¨at f¨ur Mathematik, Informatik und Naturwissenschaften der Rheinisch-Westf¨alischen Technischen Hochschule Aachen zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften genehmigte Dissertation vorgelegt von Master of Science Salih Oz¸cubuk¸cu¨ aus Gaziantep (T¨urkei) Berichter: Universit¨atsprofessor Dr. Carsten Bolm Universit¨atsprofessor Dr. Dieter Enders Tag der m¨undlichen Pr¨ufung: 22 Januar 2007 Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verf¨ugbar. For everybody The work presented in this thesis was carried out at the Institute of Organic Chemistry of the RWTH-Aachen University, under the supervision of Prof. Dr. Carsten Bolm between January 2003 and July 2006. I would like to thank Prof. Dr. Carsten Bolm for giving me the opportunity to work on this exciting research topic, excellent conditions and support in his research group. I would like to thank Prof. Dr. Dieter Enders for his kind assumption of the co-reference. Parts of this work have already been published or submitted: ’Organosilanols as Catalysts in Asymmetric Aryl Transfer Reactions’ Oz¸cubuk¸cu,¨ S.; Schmidt, F.; Bolm, C. Org. Lett. 2005, 7, 1407. (This article has been highlighted in Synfact 2005, 0, 41.) ’A General and Efficient Synthesis of Nitrogen-Substituted Ferrocenes’ Oz¸cubuk¸cu,¨ S.; Scmitt, E.; Leifert, A.; Bolm, C.; Synthesis 2007, 389.
    [Show full text]
  • Copyrighted Material
    525 Index a alcohol racemization 356, 357 acetophenone 50–53, 293, 344, 348, 443 alkali metals 398 acetoxycyclization, of 1,6-enyne 76 alkaline earth metals 398 acetylacetone 48 N-alkenyl-substituted N,S-HC ligands 349 A3 coupling reactions 231, 232 3-alkyl-3-aryloxindoles 58 acrylonitriles 69, 211, 212, 310, 348 alkyl bis(trimethylsilyloxy) methyl silanes 122 activation period 123–125 – Tamao-Kumada oxidation of 122 active species 123 2-alkylpyrrolidyl-derived formamidinium acyclic alkane 62 precursors 516 acyclic aminocarbenes 499 alkyl silyl-fluorides 209 – ligands 503 alkyl-substituted esters 210 – metalation routes 500 N-alkyl substituted NHC class 119 acyclic aminocarbene species 499 alkynes acyclic carbene chemistry 500, 516–520 – boration of 225 acyclic carbene complexes – borocarboxylation 233, 234 – in Suzuki–Miyaura crosscoupling 505 – hydrocarboxylation 234, 235 acyclic carbene–metal complexes 505 – metal-catalyzed hydrosilylation of 132 acyclic carbenes – semihydrogenation 232, 233 – characteristic feature of 503 allenes 77 – donor abilities 502 – synthesis, mechanisms 203 – ligands 502 3-allyl-3-aryl oxindoles 60 –– decomposition routes 504 allylbenzene 345 –– donor ability 502, 503 – cross-metathesis (CM) reactions of –– metalation routes of 500 510 –– structural properties 503 allylic alkylations 509 – stabilized, by lateral enamines 518 allylic benzimidate acyclic carbone ligand 519 – aza-Claisen rearrangement of 514 – in gold-catalyzed rearrangements 520 allylic substitution 220 acyclic diaminocarbenes (ADCs) 4, 5, 499
    [Show full text]
  • Development of Methods for Regioselective Introduction of Difluoromethylene Unit Using Difluorocarbene
    Development of Methods for Regioselective Introduction of Difluoromethylene Unit Using Difluorocarbene Ryo Takayama February 2018 1 Development of Methods for Regioselective Introduction of Difluoromethylene Unit Using Difluorocarbene Ryo Takayama Doctoral Program in Chemistry Submitted to the Graduate School of Pure and Applied Sciences in Partial Fulfillment of the Requirements For the Degree of Doctor of Philosophy in Science at the University of Tsukuba 2 Contents Chapter 1. General Introduction Chapter 2. Introduction of Difluoromethylene Unit into Thiocarbonyl Compounds 2-1. S-Selective Difluoromethylation of Thiocarbonyl Compounds 2-1-1. Introduction 2-1-2. Synthesis of S-Difluoromethyl Thioimidates 2-1-3. Mechanistic Study 2-1-4. Comparison with the Reported Methods for the Generation of Difluorocarbene 2-1-5. Conclusion 2-2. Difluoromethylidenation of Dithioesters: Synthesis of Sulfur-Substituted Difluoroalkenes 2-2-1. Introduction 2-2-2. Synthesis of Sulfanylated Difluoroalkenes 2-2-3. Mechanistic Study 2-2-4. Comparison with the Reported Methods for the Generation of Difluorocarbene 2-2-5. Conclusion 2-3. Experimental Section 2-4. References 3 Chapter 3. Introduction of Difluoromethylene Unit into Dienol Silyl Ethers 3-1. Regioselective Difluorocyclopropanation of Dienol Silyl Ethers 3-1-1. Introduction 3-1-2. Regioselective Difluorocyclopropanation: Synthesis of Vinylated Difluorocyclopropanes 3-1-3. Conclusion 3-2. Metal-Free Synthesis of α,α-Difluorocyclopentanone Derivatives via Regioselective Difluorocyclopropanation/VCP Rearrangement of Dienol Silyl Ethers 3-2-1. Introduction 3-2-2. Metal-Free Synthesis of 5,5-Difluorocyclopent-1-en-1yl Silyl Ethers 3-2-3. Advantages of the Organocatalytic Synthesis 3-2-4. Conclusion 3-3. Synthesis of Fluorinated Cyclopentenones via Regioselective Difluorocyclopropanation of Dienol Silyl Ethers 3-3-1.
    [Show full text]
  • Transcription 12.02.10A
    Lecture 10A • 02/10/12 Protecting groups I want to show you another common protecting group used for alcohols. It’s the formation of what are known as silyl ethers. The version that your text has is the TMS ether. Don’t get that confused with tetramethylsilane, which is our standard that we use in NMR; this is trimethylsilyl; this is very close in form. What it is – trimethylsilyl chloride is the reagent that’s generally used. When you react it with an alcohol, the silicon-chlorine bond is active enough that you’re able to do an Sn2-style reaction, even is you just have the neutral alcohol. You might notice that there’s a whole bunch of alkyl groups on the silicon; how can you do an Sn2 with something that’s got that much steric hinderance? Silicon’s larger enough that you don’t have the same form of steric crowding, so this reaction is able to take place. We have the regular form of deprotonation step afterwards. If it weren’t for the fact that we have a silicon there instead of a carbon, this would just be a regular old ether, but that’s why this is called a silyl ether. That somes from the fact that SiH4 is called silane. The -ane is actually used for other atoms besides carbon. You can have phosphane, silane – usually means add hydrogens to that particular element. Silicon can take four just like carbon because it’s in the same column of the periodic table as carbon. This particular protecting group is very widely used, but it has certain drawbacks, in that it very easily reacts in both acidic and basic media.
    [Show full text]
  • Biocatalytic Silylation: the Condensation of Phenols and Alco- Hols with Triethylsilanol
    Preprints (www.preprints.org) | NOT PEER-REVIEWED | Posted: 28 June 2021 Article Biocatalytic Silylation: The Condensation of Phenols and Alco- hols with Triethylsilanol Emily I. Sparkes,1,2 Chisom S. Egedeuzu,1,2 Billie Lias,1,2 Rehana Sung,1 Stephanie A. Caslin,1,2 S. Yasin Tabatabei Dakhili,1,2 Peter G. Taylor,3 Peter Quayle,2 Lu Shin Wong1,2* 1 Manchester Institute of Biotechnology, University of Manchester, 131 Princess Street, Manchester M1 7DN, UK 2 Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK 3 Faculty of Science, Technology, Engineering and Mathematics, Open University, Walton Hall, Milton Keynes MK7 6AA, UK * Correspondence: [email protected] Abstract: Silicatein-α (Silα), a hydrolytic enzyme derived from siliceous marine sponges, is one of the few enzymes in nature capable of catalysing the metathesis of silicon-oxygen bonds. It is there- fore of interest as a possible biocatalyst for the synthesis of organosiloxanes. To further investigate the substrate scope of this enzyme, a series of condensation reactions with a variety of phenols and aliphatic alcohols were carried out. In general, it was observed that Silα demonstrated a preference for phenols, though the conversions were relatively modest in most cases. In the two pairs of chiral alcohols that were investigated, it was found that the enzyme displayed a preference for the silyla- tion of the S-enantiomers. Additionally, the enzyme’s tolerance to a range of solvents was tested. Silα had the highest level of substrate conversion in the non-polar solvents n-octane and toluene, although the inclusion of up to 20% of 1,4-dioxane was tolerated.
    [Show full text]
  • Silicon‐Derived Singlet Nucleophilic Carbene Reagents in Organic
    Author Manuscript Title: Silicon-Derived Singlet Nucleophilic Carbene Reagents in Organic Synthesis Authors: Daniel Priebbenow This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofrea- ding process, which may lead to differences between this version and the Version of Record. To be cited as: 10.1002/adsc.202000279 Link to VoR: https://doi.org/10.1002/adsc.202000279 REVIEW DOI: 10.1002/adsc.202000279 Silicon-Derived Singlet Nucleophilic Carbene Reagents in Organic Synthesis Daniel L. Priebbenowa* a School of Chemistry, The University of Melbourne, Parkville, Victoria, Australia, 3010 [email protected] Dedicated to Prof. Dr. Carsten Bolm on the occasion of his 60th birthday. Received: Abstract. Over fifty years ago, the 1,2-rearrangement of This review aims to cover the historical literature and acyl silanes was first described by Adrian Brook and co- recent advances with regards to these valuable silicon- workers. This rearrangement (now termed the Brook based reagents and highlight additional aspects related to rearrangement) yields reactive silicon-based singlet the intriguing reactivity of both the carbene and nucleophilic carbene (SNC) intermediates that participate in oxocarbenium intermediates. a variety of chemical transformations including 1,2-carbonyl addition, 1,4-addition to electron-deficient unsaturated bonds Keywords: Organosilicon; Siloxy Carbene; Acyl and insertion into C-H and O-H bonds. Silane; Singlet Nucleophilic Carbene; Photochemistry mediated synthetic transformations. 1.0 Introduction In addition to its important physical properties, silicon also plays a valuable role in organic Silicon containing molecules have unique and [3] important physical properties that have been synthesis.
    [Show full text]
  • The Condensation of Phenols and Alcohols with Triethylsilanol
    catalysts Article Biocatalytic Silylation: The Condensation of Phenols and Alcohols with Triethylsilanol Emily I. Sparkes 1,2, Chisom S. Egedeuzu 1,2 , Billie Lias 1,2, Rehana Sung 1, Stephanie A. Caslin 1,2, S. Yasin Tabatabaei Dakhili 1,2, Peter G. Taylor 3, Peter Quayle 2 and Lu Shin Wong 1,2,* 1 Manchester Institute of Biotechnology, University of Manchester, 131 Princess Street, Manchester M1 7DN, UK; [email protected] (E.I.S.); [email protected] (C.S.E.); [email protected] (B.L.); [email protected] (R.S.); [email protected] (S.A.C.); [email protected] (S.Y.T.D.) 2 Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK; [email protected] 3 Faculty of Science, Technology, Engineering and Mathematics, Open University, Walton Hall, Milton Keynes MK7 6AA, UK; [email protected] * Correspondence: [email protected] Abstract: Silicatein-α (Silα), a hydrolytic enzyme derived from siliceous marine sponges, is one of the few enzymes in nature capable of catalysing the metathesis of silicon–oxygen bonds. It is therefore of interest as a possible biocatalyst for the synthesis of organosiloxanes. To further investigate the Citation: Sparkes, E.I.; substrate scope of this enzyme, a series of condensation reactions with a variety of phenols and Egedeuzu, C.S.; Lias, B.; Sung, R.; aliphatic alcohols were carried out. In general, it was observed that Silα demonstrated a preference Caslin, S.A.; Tabatabaei Dakhili, S.Y.; for phenols, though the conversions were relatively modest in most cases.
    [Show full text]
  • Assessing Steric Bulk of Protecting Groups Via a Computational Determination of Exact Cone Angle and Exact Solid Cone Angle
    ASSESSING STERIC BULK OF PROTECTING GROUPS VIA A COMPUTATIONAL DETERMINATION OF EXACT CONE ANGLE (θo) AND EXACT SOLID CONE ANGLE (Θo) A thesis submitted to the Kent State University Honors College in partial fulfillment of the requirements for General Honors by Julian Witold Sobieski May, 2018 Thesis written by Julian Witold Sobieski Approved by _______________________________________________________________________, Advisor _______________________________________________________________________, Chair, Department of Chemistry and Biochemistry Accepted by ___________________________________________________, Dean, Honors College ii TABLE OF CONTENTS LIST OF FIGURES ............................................................................................................iv LIST OF TABLES ..............................................................................................................v LIST OF COMMON ABBREVIATIONS .........................................................................vi ACKNOWLEDGEMENTS .............................................................................................viii CHAPTER I. INTRODUCTION ......................................................................................1 1.1: The need for organic protecting group steric descriptors .....................1 1.2: The Tolman angle ................................................................................4 1.3: Exact cone angle (θo) and exact solid cone angle (Θo) ........................6 1.4: Other literature methods for calculating
    [Show full text]
  • I. Total Synthesis of (+)-Spongiolactone and Derivatives
    I. TOTAL SYNTHESIS OF (+)-SPONGIOLACTONE AND DERIVATIVES ENABLING INITIAL STRUCTURE-ACTIVITY RELATIONSHIP STUDIES: DISCOVERY OF A MORE POTENT DERIVATIVE II. STUDIES TOWARD RECYCLABLE ISOTHIOUREA CATALYSTS A Dissertation by NATALIE LAURA HARVEY Submitted to the Office of Graduate and Professional Studies of Texas A&M University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Chair of Committee, Daniel Romo Committee Members, Daniel Singleton David Bergbreiter Thomas McKnight Head of Department, Francois Gabbai December 2015 Major Subject: Chemistry Copyright 2015 Natalie Laura Harvey ABSTRACT β-lactone containing natural products are attractive targets for total synthesis and subsequent biological studies. Given the remarkable ability of this moiety to covalently inhibit specific proteins, we were drawn to spongiolactone as a synthetic target. Through our studies, the first total synthesis of this compound was achieved along with the synthesis of several derivatives. This synthesis enabled cytotoxicity studies to be carried out against a variety of cancer cell lines, with good activity observed in the human chronic myelogenous leukemia (K562) cell line. Particularly intriguing was the discovery of a more potent derivative than the natural product itself which was then modified and taken on to activity based protein profiling (ABPP) studies. The first magnetite-supported benzotetramisole (BTM) catalyst was prepared and utilized in the kinetic resolution of secondary alcohols. Overall, the selectivity factor was lower than the parent (+)-BTM (s = 48 versus s = 148, respectively), however the resulting ester was achieved in excellent enantiomeric excess, albeit with low reaction conversion. Further studies suggest an unfavorable inactivation of the catalyst taking place in the presence of uncapped magnetite.
    [Show full text]