Copyrighted Material

Total Page:16

File Type:pdf, Size:1020Kb

Copyrighted Material Index Page numbers in bold indicate tables acetylcholinesterase 12 2-azidobiphenyls 477, 479 Acheson indole synthesis 506, 507 azirines 296–298 acid-catalyzed furan ring-opening 313–316 aeration oxygenation 549, 550 bacterial infections 4–5, 19, 76–77 Åkermark carbazole synthesis 600, 601 Baell indole synthesis 509, 510 alkyl phenylphosphonites 269 Baeyer–Jackson indole synthesis 363–364 alkyne cyclization 236, 240 Bailey–Liebeskind indole synthesis 213–216, 215 alkyne hydroamination 45–46, 55, 72 Bailey–Liebeskind–O’Shea indoline–indole synthesis 213–218 2-alkynylanilines 396–397, 400, 575–579 applications 213, 216 Allen and Weiss indole synthesis 190–191, 192, 193 Bailey–Liebeskind indole synthesis 213–216, 215 allene heteroannulation 623, 625 indoles produced 215 α-azidocinnamate esters 287–288, 293 mechanism 213, 214 α-diazoesters 450, 455 O’Shea indole synthesis 213, 216–217 Alzheimer’s disease 12 Barbier reaction 186–187 amine carbonyl ring closure 236, 239 Barluenga indole synthesis 500, 501, 528, 530, 592, 594 anilinopyridines 468, 470 Bartoli indole synthesis 121–130 anilinoquinolines 468, 470 applications 123–129 anion-sensing systems 22–24 functionalized indoles 127–128, 128–129 2-(arylamino)styrenes 673 indoles produced 121, 122 aryl azides 472, 478 Madelung indole synthesis 148, 153 1-arylcarbazoles 397, 401 mechanism 121 aryl-Heck indole-carbazole synthesis 597–599, 623, 629 modifications 121, 123, 129 arylhydrazides 67 naturally occurring indoles 123, 128 arylhydrazines 44–45, 50, 56, 57–60 pharmaceuticals containing indoles 126, 128 arylhydrazones 50, 57–58, 60–63, 66, 67 Barton-Ninomiya indole synthesis 548, 549 aryne intermediates Belley N-hydroxyindole synthesis 376, 377 Barluenga indole synthesis 528, 530 benzo[b]carbazoles 478, 480 Biehl indole synthesis 532 benzoquinone imines 206 Brown-Eastwood indole synthesis 528, 530 1,4-benzoquinones 191, 192, 193 Bunnett indole synthesis 528, 529 benzoquinones 188–205 Caubère indole synthesis 528, 529 Bergman carbazole-indole synthesis 438, 442 early indole syntheses 528, 529 Bergman cyclization 148 Greaney indole synthesis 532, 533 Bernier indole synthesis 194, 201 Greaney indoline-indole synthesis 535 β-dicarbonyl compounds 581–583 Guitán indole synthesis 528, 530 Biehl indole synthesis 532 He indole synthesis 533, 534 biindoles Iwao-Watanabe indole synthesis 528, 530 Cadogan–Sundberg indole synthesis 267, 269, 271 Kudzma indole-carbazole synthesis 528, 531, 532 copper-catalyzed indole ring synthesis 579 Larock indole synthesis 534, 535 Fischer indole synthesis 77, 102 Lin-Wang indole synthesis 532–533COPYRIGHTEDgold-catalyzed MATERIAL indole ring synthesis 640 Indoles via arynes in indole and carbazole synthesis 528–536 iridium-catalyzed indole ring synthesis 655 Sanz indole-carbazole synthesis 531, 532 Leimgruber–Batcho indole synthesis 347 Stoltz indoline-indole synthesis 535 ligands containing indoles 29 Studer indole synthesis 533, 534 materials containing indoles 21–23 Tokuyama indoline-carbazole synthesis 531, 532 Nenitzescu o,β-dinitrostyrene reductive cyclization 329 Wu-Sha indole synthesis 534–535 palladium-catalyzed indole ring synthesis 600, 607 Zhu indole synthesis 533, 534 biofouling 5 Zyryanov indoline-indole synthesis 535 biological activity of indoles 4–15 azacarbazoles 304–306 Alzheimer’s disease 12 Indole Ring Synthesis: From Natural Products to Drug Discovery, First Edition. Gordon W. Gribble. © 2016 John Wiley & Sons, Ltd. Published 2016 by John Wiley & Sons, Ltd. 0002738046.indd 676 5/23/2016 9:12:49 AM Index 677 bacterial infections 4–5 CAN see cerium(IV) ammonium nitrate cancer 8, 10–12 cancer cannabimimetics 12–13 biological activity of indoles 8, 10–12 fungal infections 5 Fischer indole synthesis 73–75, 81–82, 97 inflammation 6–7, 8, 13 materials containing indoles 27–28 neurological disorders 7–8, 9, 12 pharmaceutical indole products 15–17 obesity and diabetes 7, 9 cannabimimetics 12–13 parasitic infections 5–6 carbazoles plant growth regulators 14–15 Åkermark carbazole synthesis 600, 601 tricyclic indoles 13–14 aryl-Heck indole-carbazole synthesis 597–599, 623, 629 viral infections 5–6, 7 Bergman carbazole-indole synthesis 438, 442 Bischler indole synthesis 249–259 Buchwald–Hartwig indole synthesis 619, 620 applications 251–256 Cadogan–Sundberg indole synthesis 266–267, 269, Black indole synthesis 250–251 271, 275 Buu-Hoi indole synthesis 250 cycloaddition syntheses from vinyl pyrroles 506 cryptolepine alkaloids 255, 255 Diels–Alder cycloaddition 437–451, 453–458 indoles produced 252–253 electrocyclization 489, 490 mechanism 249–250, 258 electrocyclization of pyrroles 515 modifications 250–251, 253–258 Fujii-Ohno indole synthesis 526 Moody indole synthesis 255–256 gold-catalyzed indole ring synthesis 640, 641 Reddy indole synthesis 257, 258 Graebe–Ullmann carbazole-carboline synthesis 424–434 Yu indole synthesis 256 Knochel indole synthesis 299 Bischler–Napieralski cyclization 318, 320 Knölker carbazole synthesis 391–395 1,2-bis(diphenylphosphino)ethane (DPPE) 271 Kudzma indole-carbazole synthesis 528, 531, 532 bismuth nitrate 41 Magnus carbazole-indole synthesis 438–439, 442 Black indole synthesis 250–251, 263 mercury-catalyzed indole ring synthesis 663, 664 Blechert indole synthesis 485, 487 miscellaneous indole ring-forming syntheses 673 Boger indole synthesis 458, 461, 464, 467 miscellaneous palladium-catalyzed syntheses 623–631 Borsche–Dreschel carbazole synthesis 66, 74–75 Mohanakrishnan carbazole synthesis 515 Boruah indole synthesis 194, 197 molybdenum-catalyzed indole ring synthesis 660, 662 Bredereck’s reagent 346–347 Moody carbazole synthesis 437–440 Brown-Eastwood indole synthesis 528, 530 naturally occurring indoles 4 Bucherer carbazole synthesis 66 nitrene cyclization 265 Buchwald indole synthesis 371, 372 Nozaki carbazole synthesis 619, 620 Buchwald–Hartwig indole synthesis 619–622 oxidative cyclization 397, 401 amination with C–H activation 619, 621 Petillo carbazole synthesis 519 applications 619–621 photolysis/photochemical synthesis 468–469, 472, 474, Nozaki carbazole synthesis 619, 620 477–480 Willis indole synthesis 619, 620 Plieninger–Moody carbazole synthesis 437, 438, 440–441 Buchward synthesis 98 indoles via arynes 528–536 Bunnett-Beugelmans indole synthesis 473, 475, 478–479 pyrrolo-2,3-quinodimethanes 519 Bunnett indole synthesis 528, 529 reviews of indole-ring synthesis 34 Burger indole synthesis 140, 143 rhodium-catalyzed indole ring synthesis 632, 633 Butin indole synthesis 313–316 Rossi indole-carbazole synthesis 474, 479 applications 313–314 ruthenium-catalyzed indole ring synthesis 646 indoles produced 315 Sanz indole-carbazole synthesis 531, 532 indolo[3,2-c]quinolines 314, 316 Schmittel indole synthesis 478, 479–480 mechanism 313 Smith carbazole synthesis 477, 479 butyrylcholinesterase 12 Sundberg indole synthesis 278–280, 282, 284–285 Buu-Hoi indole synthesis 250 Täuber carbazole synthesis 301–303 Tokuyama indoline-carbazole synthesis 531, 532 Cacchi indole synthesis 615–618 carbazolones 371, 373 applications 615–617 carbenoids 236, 239 Utimoto indole synthesis 615, 616 carbolines Cadogan–Sundberg indole synthesis 266–277 annulation of oxindoles 563–565 applications 266–267, 271 aryl-Heck indole-carbazole synthesis 597 biindoles 267, 269, 271 Cadogan–Sundberg indole synthesis 266 carbazoles 266–267, 269, 271, 275 Diels–Alder cycloaddition 453–454, 458, 461 Freeman indole synthesis 267, 269, 273 gold-catalyzed indole ring synthesis 640, 642 fused indoles 272 Graebe–Ullmann carbazole-carboline synthesis 424–434 indoles produced 268, 270 intramolecular anionic cycloaromatization 489, 490 mechanism 266, 267 naturally occurring indoles 4 modifications 267, 269–274 photolysis/photochemical synthesis 468, 470, 479 side reactions 271–272, 276 Quéguiner azacarbazole synthesis 304, 306 0002738046.indd 677 5/23/2016 9:12:49 AM 678 Index carbolines (Cont’d) Diels–Alder cycloaddition 437–463, 506–510, 517–519 reviews of indole-ring synthesis 34 dipolar cycloaddition 483–486 ruthenium-catalyzed indole ring synthesis 646 Eguchi indole synthesis 506, 508 Sundberg indole synthesis 280, 284 electrocyclization 488–489, 491, 512–516 Castro–Stephens indole synthesis 575–577 Harman indole synthesis 509 catalytic dehydrogenation Hiremath-Schneller indole synthesis 506, 507 Barton-Ninomiya indole synthesis 548, 549 intramolecular anionic cycloaromatization 489, 490 chloranil 539, 541, 545 Jones indole synthesis 506, 507 Clive indoline dehydrogenation 539, 540 Muchowski indole synthesis 506, 508 Davies indole synthesis 520, 521 Murase indole synthesis 506–507, 508 2,3-dichloro-5,6-dicyano-1,4-benzoquinone 520–523, 539, Noland indole synthesis 506, 507 541–545 Pauson–Khand reaction 660, 661 Gribble indoline dehydrogenation 539, 540 photochemical synthesis of indoles and carbazoles 468–482 Inada indole synthesis 547, 549 platinum-catalyzed indole ring synthesis 649 indolines 539–552 Plieninger indole synthesis 464–467 manganese dioxide 544–546, 548 pyrroles 512–516 Matsumoto indole synthesis 520, 521 pyrrolo-2,3-quinodimethanes 517–519 Murakami indole synthesis 520, 522 Seitz indole synthesis 506, 508 Naito indoline dehydrogenation 539, 540 sigmatropic rearrangements 487–491 palladium and palladium-charcoal catalysts 520–521, 523, Tao indole synthesis 507, 508 539–541 vinyl pyrroles 506–511 pyrroles 520–524 Yamashita indole synthesis 507, 509 Remers indole synthesis 520, 521 Yoshida-Yanagisawa indole synthesis 509, 510 Saito indole synthesis 520, 522 cyclooxygenase (COX) inhibitors 6–7, 77–80 selenium-catalysts 548, 549–550
Recommended publications
  • Synthesis of Indole and Oxindole Derivatives Incorporating Pyrrolidino, Pyrrolo Or Imidazolo Moieties
    From DEPARTMENT OF BIOSCIENCES AT NOVUM Karolinska Institutet, Stockholm, Sweden SYNTHESIS OF INDOLE AND OXINDOLE DERIVATIVES INCORPORATING PYRROLIDINO, PYRROLO OR IMIDAZOLO MOIETIES Stanley Rehn Stockholm 2004 All previously published papers have been reproduced with permission from the publishers. Published and printed by Karolinska University Press Box 200, SE-171 77 Stockholm, Sweden © Stanley Rehn, 2004 ISBN 91-7140-169-5 Till Amanda Abstract The focus of this thesis is on the synthesis of oxindole- and indole-derivatives incorporating pyrrolidins, pyrroles or imidazoles moieties. Pyrrolidino-2-spiro-3’-oxindole derivatives have been prepared in high yielding three-component reactions between isatin, α-amino acid derivatives, and suitable dipolarophiles. Condensation between isatin and an α-amino acid yielded a cyclic intermediate, an oxazolidinone, which decarboxylate to give a 1,3-dipolar species, an azomethine ylide, which have been reacted with several dipolarophiles such as N- benzylmaleimide and methyl acrylate. Both N-substituted and N-unsubstituted α- amino acids have been used as the amine component. 3-Methyleneoxindole acetic acid ethyl ester was reacted with p- toluenesulfonylmethyl isocyanide (TosMIC) under basic conditions which gave (in a high yield) a colourless product. Two possible structures could be deduced from the analytical data, a pyrroloquinolone and an isomeric ß-carboline. To clarify which one of the alternatives that was actually formed from the TosMIC reaction both the ß- carboline and the pyrroloquinolone were synthesised. The ß-carboline was obtained when 3-ethoxycarbonylmethyl-1H-indole-2-carboxylic acid ethyl ester was treated with a tosylimine. An alternative synthesis of the pyrroloquinolone was performed via a reduction of a 2,3,4-trisubstituted pyrrole obtained in turn by treatment of a vinyl sulfone with ethyl isocyanoacetate under basic conditions.
    [Show full text]
  • Visible Light Photoredox Catalysis with Transition Metal Complexes: Application in Organic Synthesis
    Visible Light Photoredox Catalysis with Transition Metal Complexes: Application in Organic Synthesis Penghao Chen Dong Group Seminar April, 10th, 2013 Introduction Kalyanasundaram, K. Coord. Chem. Rev. 1982, 46, 159 Introduction Stern‐Volmer Relationship Turro, N. J. Modern Molecular Photochemistry; Benjamin/Cummings: Menlo Park, CA, 1978. Stoichiometric Net Reductive Reactionreductant1. Reduction is required of Electron Poor Olefin O Bn NH2 2 Pac, C. et. al., J. Am. Chem. Soc. 1981, 103, 6495 Net Reductive Reaction 2. Reductive Dehalogenation Fukuzumi, S. et. al., J. Phys. Chem. 1990, 94, 722. Net Reductive Reaction 2. Reductive Dehalogenation Stephenson, C. R. J. et. al., J. Am. Chem. Soc. 2009, 131, 8756. Stephenson, C. R. J. et. al., Nature Chem. 2012, 4, 854 Net Reductive Reaction 3. Radical Cyclization Stephenson, C. R. J. et. al., Chem. Commun. 2010, 46, 4985 Stephenson, C. R. J. et. al., Nature Chem. 2012, 4, 854 Net Reductive Reaction 4. Epoxide and Aziridine Opening Fensterbank, L. et. al., Angew. Chem., Int. Ed. 2011, 50, 4463 Hasegawa, E. et. al., Tetrahedron 2006, 62, 6581 Guindon, Y. et. al., Synlett 1998, 213 Guindon, Y. et. al., Synlett 1995, 449 Net Oxidative Reaction 1. Functional Group Reactions Cano‐Yelo, H.; Deronzier, A. Tetrahedron Lett. 1984, 25, 5517 Net Oxidative Reaction 1. Functional Group Reactions Jiao, N. et. al., Org. Lett. 2011, 13, 2168 Net Oxidative Reaction 1. Functional Group Reactions Jørgensen, K. A.; Xiao, W.‐J. Angew. Chem., Int. Ed. 2012, 51, 784 Net Oxidative Reaction 2. Oxid. Generation of Iminium Ions Stephenson, C. R. J. et. al., J. Am. Chem. Soc. 2010, 132, 1464 Net Oxidative Reaction 2.
    [Show full text]
  • Priya Mathew
    PROGRESS TOWARDS THE TOTAL SYNTHESIS OF MITOMYCIN C By Priya Ann Mathew Dissertation Submitted to the Faculty of the Graduate School of Vanderbilt University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY in Chemistry August, 2012 Nashville, Tennessee Approved: Professor Jeffrey N. Johnston Professor Brian O. Bachmann Professor Ned A. Porter Professor Carmelo J. Rizzo ACKNOWLEDGMENTS I would like to express my gratitude to everyone who made my graduate career a success. Firstly, I would like to thank my advisor, Professor Jeffrey Johnston, for his dedication to his students. He has always held us to the highest standards and he does everything he can to ensure our success. During the challenges we faced in this project, he has exemplified the true spirit of research, and I am especially grateful to him for having faith in my abilities even when I did not. I would like to acknowledge all the past and present members of the Johnston group for their intellectual discussion and their companionship. In particular, I would like to thank Aroop Chandra and Julie Pigza for their incredible support and guidance during my first few months in graduate school, Jayasree Srinivasan who worked on mitomycin C before me, and Anand Singh whose single comment “A bromine is as good as a carbon!” triggered the investigations detailed in section 2.6. I would also like to thank the other members of the group for their camaraderie, including Jessica Shackleford and Amanda Doody for their friendship, Hubert Muchalski for everything related to vacuum pumps and computers, Michael Danneman and Ken Schwieter for always making me laugh, and Matt Leighty and Ki Bum Hong for their useful feedback.
    [Show full text]
  • Dppm-Derived Phosphonium Salts and Ylides As Ligand Precursors for S-Block Organometallics
    Issue in Honor of Prof. Rainer Beckert ARKIVOC 2012 (iii) 210-225 Dppm-derived phosphonium salts and ylides as ligand precursors for s-block organometallics Jens Langer,* Sascha Meyer, Feyza Dündar, Björn Schowtka, Helmar Görls, and Matthias Westerhausen Institute of Inorganic and Analytical Chemistry, Friedrich-Schiller-University Jena Humboldtstraße 8, D-07743 Jena, Germany E-mail: [email protected] Dedicated to Professor Rainer Beckert on the Occasion of his 60th Birthday DOI: http://dx.doi.org/10.3998/ark.5550190.0013.316 Abstract The addition reaction of 1,1-bis(diphenylphosphino)methane (dppm) and haloalkanes R-X yields the corresponding phosphonium salts [Ph2PCH2PPh2R]X (1a: R = Me, X = I; 1b: R = Et, X = Br; 1c: R = iPr, X = I; 1d: R = CH2Mes, X = Br; 1e: R = tBu, X = Br). In case of the synthesis of 1e, [Ph2MePH]Br (3) was identified as a by-product. Deprotonation of 1 by KOtBu offers access to the corresponding phosphonium ylides [Ph2PCHPPh2R] (2a: R = Me; 2b: R = Et; 2c: R = iPr; 2d: R = CH2Mes) in good yields. Further deprotonation of 2a using n-butyllithium allows the isolation of the lithium complex [Li(Ph2PCHPPh2CH2)]n (4) and its monomeric tmeda adduct [(tmeda)Li(Ph2PCHPPh2CH2)] (4a). All compounds were characterized by NMR measurements and, except of 4, by X-ray diffraction experiments. Keywords: Phosphonium salt, phosphonium ylide, lithium, lithium phosphorus coupling Introduction Phosphonium ylides gained tremendous importance in organic chemistry, since Wittig and co- workers developed their alkene synthesis in the
    [Show full text]
  • Nitrogen, Oxygen and Sulfur Ylide Chemistry; Edited by JS Clark
    1134 BOOKREVIEW Nitrogen, Oxygen and Sulfur Ylide Chemistry; edited fer protocol midway through. In addition to the carbene- by J. S. Clark; Oxford University Press: Oxford, 2002; and carbenoid-mediated methods in this chapter, two sec- hardback, £80.00, pp 292, ISBN 0-19-850017-3. tions by Sato deal with the desilylation of α-silylated ammonium and sulfonium salts. Ammonium and sulfonium ylides have been recognised The following chapter, on azomethine, carbonyl and thio- and utilised as intermediates in various reactions since carbonyl ylides, encompasses a wider range of synthetic the discovery of the Stevens rearrangement some sev- methods. In addition to the use of diazo compounds in enty-five years ago. In the past two or three decades, both intra- and intermolecular reactions, there are sec- however, the field has undergone a rapid expansion and tions on the generation of azomethine ylides by conden- now incorporates many useful transformations of oxo- sation of amines with aldehydes and by oxidation of nium, as well as ammonium and sulfonium ylides. The bis(silylmethyl)amines, and on the generation of carbo- reasons for this expansion are twofold – firstly, there has nyl ylides by reduction of bis(chloroalkyl)ethers. The been a recognition of the power and versatility of these final short chapter, on nitrile ylide chemistry, covers two intermediates for synthesis of complex organic mole- methods: the reaction of nitriles with metal carbenes and cules; and secondly, catalytic methods for their genera- the thermolysis of oxazaphospholines. tion have been developed which are milder, cleaner and Overall, the book achieves its aim of providing a useful more flexible than the traditional method of salt deproto- introduction to modern practical methods in ylide chem- nation.
    [Show full text]
  • The Synthesis of Tryptophan Derivatives, 2
    Graduate Theses, Dissertations, and Problem Reports 2009 The synthesis of tryptophan derivatives, 2- and/or 3-substituted indoles, progress toward dilemmaones A-C, and synthetic studies towards fistulosin via palladium-catalyzed reductive N- heteroannulation Christopher Andrew Dacko West Virginia University Follow this and additional works at: https://researchrepository.wvu.edu/etd Recommended Citation Dacko, Christopher Andrew, "The synthesis of tryptophan derivatives, 2- and/or 3-substituted indoles, progress toward dilemmaones A-C, and synthetic studies towards fistulosin via palladium-catalyzed reductive N-heteroannulation" (2009). Graduate Theses, Dissertations, and Problem Reports. 4454. https://researchrepository.wvu.edu/etd/4454 This Dissertation is protected by copyright and/or related rights. It has been brought to you by the The Research Repository @ WVU with permission from the rights-holder(s). You are free to use this Dissertation in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you must obtain permission from the rights-holder(s) directly, unless additional rights are indicated by a Creative Commons license in the record and/ or on the work itself. This Dissertation has been accepted for inclusion in WVU Graduate Theses, Dissertations, and Problem Reports collection by an authorized administrator of The Research Repository @ WVU. For more information, please contact [email protected]. The Synthesis of Tryptophan Derivatives, 2- and/or 3- Substituted Indoles, Progress Toward Dilemmaones A-C, and Synthetic Studies Towards Fistulosin via Palladium-Catalyzed Reductive N-Heteroannulation Christopher Andrew Dacko Dissertation submitted to the Eberly College of Arts and Sciences at West Virginia University in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry Björn C.
    [Show full text]
  • Chapter16.Pdf
    (9-11/94)(2,3/97)(12/05)(1-6/06) Neuman Chapter 16 Chapter 16 Addition and Substitution Reactions of Carbonyl Compounds from Organic Chemistry by Robert C. Neuman, Jr. Professor of Chemistry, emeritus University of California, Riverside [email protected] <http://web.chem.ucsb.edu/~neuman/orgchembyneuman/> Chapter Outline of the Book ************************************************************************************** I. Foundations 1. Organic Molecules and Chemical Bonding 2. Alkanes and Cycloalkanes 3. Haloalkanes, Alcohols, Ethers, and Amines 4. Stereochemistry 5. Organic Spectrometry II. Reactions, Mechanisms, Multiple Bonds 6. Organic Reactions *(Not yet Posted) 7. Reactions of Haloalkanes, Alcohols, and Amines. Nucleophilic Substitution 8. Alkenes and Alkynes 9. Formation of Alkenes and Alkynes. Elimination Reactions 10. Alkenes and Alkynes. Addition Reactions 11. Free Radical Addition and Substitution Reactions III. Conjugation, Electronic Effects, Carbonyl Groups 12. Conjugated and Aromatic Molecules 13. Carbonyl Compounds. Ketones, Aldehydes, and Carboxylic Acids 14. Substituent Effects 15. Carbonyl Compounds. Esters, Amides, and Related Molecules IV. Carbonyl and Pericyclic Reactions and Mechanisms 16. Carbonyl Compounds. Addition and Substitution Reactions 17. Oxidation and Reduction Reactions 18. Reactions of Enolate Ions and Enols 19. Cyclization and Pericyclic Reactions *(Not yet Posted) V. Bioorganic Compounds 20. Carbohydrates 21. Lipids 22. Peptides, Proteins, and α−Amino Acids 23. Nucleic Acids **************************************************************************************
    [Show full text]
  • Synthesis and Photochemistry of New Carbene Precursors
    SYNTHESIS AND PHOTOCHEMISTRY OF NEW CARBENE PRECURSORS A Senior Honors Thesis Presented in Partial Fulfillment of the Requirements for graduation with distinction in Chemistry in the undergraduate colleges of The Ohio State University By Christopher M. Cassara ***** The Ohio State University June 2005 Project Advisor: Professor Matthew S. Platz, Department of Chemistry ABSTRACT Carbenes are neutral divalent reactive intermediates containing a carbon atom surrounded by only six valence electrons. Because of this electron deficiency, carbenes are very short-lived intermediates and react with a variety of functional groups. One of the most commonly used applications of carbenes is in cyclopropane synthesis. This research has focused on the synthesis of new, novel carbene precursors and the study of their photochemistry. The purpose of this research is twofold: 1) to trap the carbene with pyridine and characterize the UV spectra of the carbene ylide intermediate and 2) to determine the lifetimes and reaction rates of carbenes with various reagents. The lifetime of the carbene and the rate of its reaction with alkenes will be used to form a better understanding of the relationship between carbene structure and reactivity. Laser Flash Photolysis (LFP) techniques were used to generate the carbene, which subsequently reacted with pyridine to form an ylide. This reaction was necessary because we were not able to detect the carbene directly. The carbenes being studied cannot be directly detected because they do not exhibit a UV chromophore at or above 300 nm. Trapping the carbene with pyridine yields a species with a strong UV absorbtion at 480 nm, which is easily detected.
    [Show full text]
  • Mitomycins Syntheses: a Recent Update
    Mitomycins syntheses: a recent update Jean-Christophe Andrez Review Open Access Address: Beilstein Journal of Organic Chemistry 2009, 5, No. 33. Department of Chemistry, University of British Columbia, 2036 Main doi:10.3762/bjoc.5.33 Mall, Vancouver, BC, V6T1Z1, Canada Received: 09 January 2009 Email: Accepted: 28 May 2009 Jean-Christophe Andrez - [email protected] Published: 08 July 2009 Editor-in-Chief: J. Clayden Keywords: antitumour; bioactivity; mitomycin; mitosene; synthesis © 2009 Andrez; licensee Beilstein-Institut. License and terms: see end of document. Abstract Mitomycins are a class of very potent antibacterial and anti-cancer compounds having a broad activity against a range of tumours. They have been used in clinics since the 1960’s, and the challenges represented by their total synthesis have challenged generations of chemists. Despite these chemical and medicinal features, these compounds, in racemic form, have succumbed to total synthesis only four times over the last 30 years. Review Introduction The mitomycins pose unique challenges to the synthetic their apparent fragility, mitomycins were rapidly identified to chemist. As S. Danishefsky noted, “The complexity of the act as prodrugs and their unique activity was thought to problem arises from the need to accommodate highly inter- originate from their ability to transform in vivo to generate the active functionality in a rather compact matrix and to orches- active metabolite. This was followed by decades of investiga- trate the chemical progression such as to expose and maintain tions to understand in detail their singular mode of action. It vulnerable structural elements as the synthesis unfolds. The was found that the aziridine played a crucial role, allowing an synthesis of a mitomycin is the chemical equivalent of walking irreversible bis-alkylation of DNA [3].
    [Show full text]
  • Novel Synthesis of TV-Heterocycles
    Novel Synthesis of TV-Heterocycles A thesis submitted to Cardiff University by Damian Gordon Dunford BSc (Hons.) A thesis submitted for the Degree of Doctor of Philosophy December 2010 School of Chemistry Cardiff University UMI Number: U516902 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. Dissertation Publishing UMI U516902 Published by ProQuest LLC 2013. Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code. ProQuest LLC 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106-1346 DECLARATION This work has not previously been accepted in substance for any degree and is not concurrently submitted in candidature for any degree. Signed ..................... (candidate) Date . I ^ STATEMENT 1 This thesis is being submitted in partial fulfillment of the requirements for the degree of PhD Signed. 2) 22. .......................(candidate) Date . STATEMENT 2 This thesis is the result of my own independent work/investigation, except where otherwise stated. Other sources are acknowledged by explicit references. Signed... J <2 .. ‘. .O .V (candidate) Date STATEMENT 3 I hereby give consent for my thesis, if accepted, to be available for photocopying and for inter-library loan, and for the title and summary to be made available to outside organisations.
    [Show full text]
  • N-Glycosyl Aza-Ylides As Intermediates in the Synthesis of Novel N-Glycosides
    N-Glycosyl Aza-Ylides as Intermediates in the Synthesis of Novel N-Glycosides by Andrew Thomas Murrin Submitted in Partial Fulfillment of the Requirements for the Degree of Master of Science in the Chemistry Program YOUNGSTOWN STATE UNIVERSITY May 2020 N-Glycosyl Aza-Ylides as Intermediates in the Synthesis of Novel N-Glycosides Andrew Thomas Murrin I hereby release this thesis to the public. I understand this thesis will be made available from the OhioLINK ETD Center and the Maag Library Circulation Desk for public access. I also authorize the University and other individuals to make copies of this thesis as needed for scholarly research. Signature: ____________________________________________________________________ Andrew Thomas Murrin, Student Date Approvals: ____________________________________________________________________ Dr. Peter Norris, Thesis Advisor Date ____________________________________________________________________ Dr. John A. Jackson, Committee Member Date ____________________________________________________________________ Dr. Nina V. Stourman, Committee Member Date ____________________________________________________________________ Dr. Salvatore A. Sanders, Dean of Graduate Studies Date iii Thesis Abstract Carbohydrates are ubiquitous biological molecules that facilitate a wide array of cellular processes. Generation of libraries of carbohydrate analogues, as well as developing a complete understanding of their underlying synthetic mechanisms, are therefore imperative in advancing this field of research. This
    [Show full text]
  • 1. the Wittig Reaction
    Dr. P. Wipf Chem 2320 2/12/2007 I. Basic Principles I-I. Wittig Reaction 1. The Wittig Reaction Reviews: - Nicolaou, K. C.; Härter, M. W.; Gunzner, J. L.; Nadin, A. Liebigs Ann./Recueil 1997, 1283. - Vedejs, E.; Peterson, M. J. Top. Stereochem. 1994, 21, 1-157. - Bestmann, H. J.; Zimmerman, R. In Comprehensive Organic Synthesis; B. M. Trost and I. Fleming, Ed.; Pergamon Press: Oxford, 1991; Vol. 6; pp 171. - Schlosser, Top. Stereochem. 1970, 5, 1. First report: 1953, Wittig and Geissler, Liebigs Ann. 1953, 580, 44. 1 Dr. P. Wipf Chem 2320 2/12/2007 Industrial preparation of Vitamin A (BASF, 1956) Reagent control of Z/E-selectivity: Over much of its history, the Wittig reaction has been described as a stepwise ionic process. The hypothetical betaine intermediates were never observed, but lithium halide adducts could be isolated in some of the early Wittig experiments. The newest hypothesis attributes stereoselectivity to a combination of steric effects and varying degrees of rehybridization at phosphorous in the formation of the covalent oxaphosphetane. 2 Dr. P. Wipf Chem 2320 2/12/2007 Evidence against this mechanism started to accumulate in the late 1960's. First, the solvent dependence of the Wittig reaction did not concur with a charged intermediate, the betaine. Also, it was found that the oxaphosphetane was actually more stable than the putative betaine. Experimental and theoretical insights can be summarized as follows: 1. Under salt-free, aprotic conditions, ylides Ph3P=CHR (R=alkyl, alkenyl, phenyl) react with aldehydes to produce the oxaphosphetane directly via four-centered transition states.
    [Show full text]