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Synthesis of 4-Phosphono Β-Lactams and Related Azaheterocyclic Phosphonates

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SYNTHESIS OF 4-PHOSPHONO β-LACTAMS AND RELATED AZAHETEROCYCLIC PHOSPHONATES IR . KRISTOF MOONEN To Elza Vercauteren Promotor: Prof. dr. ir. C. Stevens Department of Organic Chemistry, Research Group SynBioC Members of the Examination Committee: Prof. dr. ir. N. De Pauw (Chairman) Prof. dr. J. Marchand-Brynaert Prof. dr. A. Haemers Prof. dr. S. Van Calenbergh Prof. dr. ir. E. Vandamme Prof. dr. ir. R. Verhé Prof. dr. ir. N. De Kimpe Dean: Prof. dr. ir. H. Van Langenhove Rector: Prof. dr. P. Van Cauwenberge IR . KRISTOF MOONEN SYNTHESIS OF 4-PHOSPHONO β-LACTAMS AND RELATED AZAHETEROCYCLIC PHOSPHONATES Thesis submitted in fulfillment of the requirements for the degree of Doctor (PhD) in Applied Biological Sciences: Chemistry Dutch translation of the title: Synthese van 4-fosfono-β-lactamen en aanverwante azaheterocyclische fosfonaten ISBN-Number: 90-5989-129-5 The author and the promotor give the authorisation to consult and to copy parts of this work for personal use only. Every other use is subject to the copyright laws. Permission to reproduce any material contained in this work should be obtained from the author. Woord Vooraf Toen ik op een hete dag in de voorbije zomer dit woord vooraf schreef, stond ik voor één van de laatste horden te nemen in de weg naar het “doctoraat”. Het ideale moment voor een nostalgische terugblik op een zeer fijne periode, hoewel het onzinnig zou zijn te beweren dat alles rozegeur en maneschijn was. En op het einde van de rit komt dan ook het moment waarop je eindelijk een aantal mensen kunt bedanken, omwille van sterk uiteenlopende redenen. Te beginnen met de mensen met wie ik het geluk heb gehad intensief te mogen samenwerken in één of meerdere onderzoeksprojecten. Ellen, Davy en Nicolai, voor mij zijn dit de meest verrijkende momenten geweest in de voorbije vier jaar. Het uitwisselen van ideeën en meningen heeft voor een zekere “drive” gezorgd die me toeliet elke morgen met vernieuwde krachten het lab in te stappen. Ik denk dat we fier kunnen zijn op de bereikte resultaten! Ook van harte bedankt aan mijn promotor, professor Chris Stevens. We hebben meerdere malen met onze handen in het haar gezeten omwille van de rare kronkels van de chemie en het onderzoeksproject is uiteindelijk helemaal anders uitgedraaid dan het initieel was voorzien. Ik hoop alleszins dat de bereikte resultaten een stevige basis kunnen vormen voor je verdere onderzoek rond azaheterocyclische fosfonaten. De collega’s hebben gezorgd voor de goede sfeer, ook buiten de standaard chemische bezigheden. Volleybal, voetbal, film, bbq’s, talloze trouwfeesten (en het voorbereiden van de bijbehorende cadeaus) en noem maar op. Bedankt Thomas, Bart, Inge, Tina, Guido, Nicola, An, Sven M., Matthias, Bert, Nicolai, Davy, Griet, Dominick, Sven C., Berten, Yves, Jan, Eva, Kurt, Diederica, Mirjana, Laurent, Viviane, Sandra en Pieter. Ook meer in het bijzonder aan mijn bureaugenoten: Ellen, David, Willem en Bram! Mijn appreciatie gaat ook uit naar de i thesisstudenten die mij als hun begeleider moeten verdragen hebben: Wouter, Vicky, Annelies, Bart, Miet en Steve. We komen elkaar vast nog wel eens tegen. Ook bedankt aan Prof. Waroquier, Veronique en Karen van het “Center for Molecular Modeling” . Samenwerken tussen sterk gespecialiseerde mensen is niet gemakkelijk. Het heeft een tijd geduurd, maar in the end kunnen we fier zijn op het resultaat! Also many thanks to prof. Zhdankin and his colleagues for their kind help with the x- ray analyses. Tenslotte kom ik bij de mensen die alles van op de eerste rij hebben meegemaakt, misschien soms zonder te begrijpen waarrond het eigenlijk altijd draaide. Het was niet gemakkelijk om al die verhalen te volgen, maar ik hoop dat vandaag alles misschien iets duidelijker of concreter wordt. Als jullie de draad toch verliezen, onthou dan maar dat het au fond gewoon gaat om spelen met molecuultjes. Veel belangrijker was jullie rol buiten de chemie, bij die dingen die zorgen voor een stabiel evenwicht in leven en werk, zoals vriendschap, een goede babbel, een gezellig thuiskomen, hulp in noodgevallen en de ongelofelijke steun bij alles wat we ondernemen! Daarom, aan mijn ondertussen sterk uitgebreide en nog steeds groeiende familie - Miriam, Tom, Ingrid, Peter, Astrid, Katrien, Arne, Stefaan, Bert, Yvette, Katleen, Kris, Myriam en Cesar - bedankt voor alles wat is geweest en nog moet komen. Tenslotte nog een woordje voor Vera, alias Bera Ban . We varen al een tijd in hetzelfde schuitje en veel van de gebeurtenissen en gevoelens die hierboven beschreven staan, hebben we samen beleefd. Professioneel zijn onze wegen ondertussen uit elkaar gegaan en dat geeft misschien aanleiding tot meer gevarieerde gesprekken, ‘s avonds aan tafel: we hebben nu elk ons verhaal van de dag te vertellen. Ik sta hier nu met en dankzij jouw steun. Ik ben er zeker van dat we binnen een paar jaar hier weer staan, maar dan met de rollen omgekeerd! Kristof Moonen 29 september 2006 ii Table of Contents Woord Vooraf i Table of Contents iii List of Abbreviations vii Chapter 1: Introduction and Goal 1 1 Biological importance of amino phosphonates 1 2 Goal of the current research 4 Chapter 2: Literature Overview on Azaheterocyclic Phosphonates 9 1 Four membered rings: azetidines and azetidinones 9 1.1 Ring closure by nucleophilic substitution 9 1.2 Nucleophilic phosphorylation 11 1.3 Cycloaddition 13 2 Five membered rings – pyrrolidines, pyrrolines and pyrrolidinones 14 2.1 Ring closure by nucleophilic substitution 15 2.2 Nucleophilic phosphorylation 15 2.3 Electrophilic phosphorylation 17 2.4 Ring closure by nucleophilic addition 19 2.5 Cycloaddition 23 2.6 Addition to cyclic imines 26 2.7 Miscellaneous 28 iii Chapter 3: Results and Discussion 31 1 Synthesis of α-aminoalkyl phosphonates 31 1.1 Introduction 31 1.2 Phosphonylation using dialkyl trimethylsilyl phosphite 35 1.3 Regioselectivity of dialkyl trimethylsilyl phosphite addition 36 1.3.1 Addition of DAPTMS to α,β-unsaturated imines 36 1.3.2 Spectroscopic characteristics of PAP’s 196 40 1.3.3 Mechanistic investigation of the double DAPTMS addition to imines 43 1.3.4 What about trialkyl phosphites? 51 1.3.5 Diphosphonic acids 54 1.3.6 Biological perspectives 57 1.4 Direct phosphonylation of aldimines with dialkyl phosphites 59 1.5 Conclusion 62 2 Synthesis of 4-phosphono β-lactams 64 2.1 Introduction 64 2.2 Preparation of N-chloroacetyl 1-aminoalkyl phosphonates 71 2.2.1 Acylation of 1-aminoalkyl phosphonates 71 2.2.2 One-pot phosphonylation of N-acyliminium ions 73 2.2.3 Conclusion 80 2.3 Ring closure towards 4-phosphono β-lactams 82 2.4 Origin of regioselectivity towards four-membered phosphono lactams 86 2.4.1 Structural properties of the substrate 88 2.4.2 HSAB considerations 91 2.4.3 Geometry of the allyl anion 95 2.4.4 Transition state conformation 98 2.5 Biological evaluation of 4-phosphono β-lactam dialkyl esters 102 2.6 Conclusion 103 3 Synthesis of 2-phosphono pyrroles 104 3.1 Introduction 104 3.2 Benzylation of α-aminoalkenyl phosphonates 107 3.3 Ring closure to 2-phosphono 3-pyrrolines 111 3.4 Ring closure – oxidation to 2-phosphono pyrroles 113 3.5 Spectral characteristics of 2-phosphono pyrroles 117 3.6 Evaluation of the preparation of bicyclic phosphono β-lactams via RCM 117 3.7 Conclusion 118 4 Synthesis of tricyclic phosphono pyrrolidines 120 4.1 Introduction 120 4.2 Synthesis and structural characterization 120 4.3 Conclusion 126 iv Chapter 4: Experimental Procedures 127 1 Instrumental Material 127 1.1 Column Chromatography 127 1.2 NMR Spectroscopy 127 1.3 Mass Spectrometry 127 1.4 Infrared Spectrometry 127 1.5 Gas Chromatography 128 1.6 Dry Solvents 128 1.7 Melting Point 128 2 Synthesis of aldimines 128 3 Synthesis of α-aminoalkyl phosphonates 132 3.1 Phosphonylation using dialkyl trimethylsilyl phosphite 132 3.2 Preparation of 3-phosphonyl-1-aminoalkyl phosphonates 135 3.2.1 General procedure for the preparation of DAPTMS 135 3.2.2 Preparation of 3-phosphonyl aminoalkyl phosphonates (PAP’s) 135 3.2.3 Preparation of 2-isopropylamino-4-phenylbut-3-ene nitrile (198) 142 3.2.4 Preparation of dimethyl 3-phenyl-2-propenyl phosphonate (210) 143 3.2.5 Preparation of diethyl (3-oxo-1-phenylpropyl) phosphonate (217) 143 3.2.6 Preparation of PAP’s using trialkyl phosphites 144 3.2.7 Preparation of diphosphonic acids 146 3.3 Phosphonylation using dialkyl phosphite 148 3.4 Preparation of monoalkyl aminoalkyl phosphonates 159 4 Synthesis of 4-phosphono β-lactams 160 4.1 Acylation of 1-aminoalkyl phosphonates 160 4.2 One-pot phosphonylation of N-acyliminium ions 166 4.2.1 General procedure 166 4.2.2 Side products 169 4.2.3 Preparation of 3-imino-1-phenylpropyl phosphonates 170 4.2.4 Preparation of 3-(chloroacetylalkylamino)-1-phenylprop-2-enyl phosphonates (267b-d) 171 4.3 Synthesis of 4-phosphono β-lactams 173 4.3.1 Typical procedure for the synthesis of 4-phosphono-β-lactams 23 173 4.3.2 Hydrogenation of diethyl 1-benzyl-4-oxo-2-(2-phenylethyl)-2-azetidinyl phosphonate (273) 177 4.3.3 Preparation of dimethyl 1-allyl-6-oxo-2-(( E)-phenylethenyl)piperidin-2-yl phosphonate (24) 178 4.4 Origin of the regioselectivity towards four-membered phosphono lactams 178 4.4.1 Preparation of benzylbut-2-enylideneamine (19o) 178 4.4.2 Preparation of dimethyl ( 2E )-1-(benzylchloroacetylamino)but-2-enyl phosphonate (21q) 179 v 4.4.3 Preparation of diethyl [benzylchloroacetylamino][(1R,5 S)-6,6- dimethylbicyclo[3.1.1]hept-2-en-2-yl]methyl phosphonate (21p) 180 4.4.4 Preparation of diethyl [1-benzyl-2-(6,6-dimethyl-bicyclo[3.1.1]hept-2-en-2-yl)-4- oxo-azetidin-2-yl] phosphonate (23l) 181
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    Federal Register / Vol. 72, No. 191 / Wednesday, October 3, 2007 / Notices 56347 B. Tips for Preparing Your Comments. under review and the receipt of notices comment, EPA recommends that you When submitting comments, remember of commencement to manufacture those include your name and other contact to: chemicals. This status report, which information in the body of your • Identify the subject by docket covers the period from August 3, 2007 comment and with any disk or CD ROM number and other identifying to September 7, 2007, consists of the you submit. If EPA cannot read your information (subject heading, Federal PMNs and TMEs, both pending or comment due to technical difficulties Register date and page number). expired, and the notices of and cannot contact you for clarification, • Follow directions—The agency may commencement to manufacture a new EPA may not be able to consider your ask you to respond to specific questions chemical that the Agency has received comment. Electronic files should avoid or organize comments by referencing a under TSCA section 5 during this time the use of special characters, any form Code of Federal Regulations (CFR) part period. of encryption, and be free of any defects or section number. DATES: Comments identified by the or viruses. For additional information • Explain why you agree or disagree; specific PMN number or TME number, about EPA’s public docket, visit the EPA suggest alternatives and substitute must be received on or before November Docket Center homepage at http:// language for your requested changes. 2, 2007. www.epa.gov/epahome/dockets.htm. • Docket: All documents in the docket Describe any assumptions and ADDRESSES: Submit your comments, provide any technical information and/ identified by docket identification (ID) are listed in the docket’s index available or data that you used.
  • NMR Studies of Phosphorus Ligand Complexes of Silver and Cobalt Steven Mark Socol Iowa State University

    NMR Studies of Phosphorus Ligand Complexes of Silver and Cobalt Steven Mark Socol Iowa State University

    Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1983 NMR studies of phosphorus ligand complexes of silver and cobalt Steven Mark Socol Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Inorganic Chemistry Commons Recommended Citation Socol, Steven Mark, "NMR studies of phosphorus ligand complexes of silver and cobalt " (1983). Retrospective Theses and Dissertations. 8962. https://lib.dr.iastate.edu/rtd/8962 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. INFORMATION TO USERS This reproduction was made from a copy of a document sent to us for microfilming. While the most advanced technology has been used to photograph and reproduce this document, the quality of the reproduction is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help clarify markings or notations which may appear on this reproduction. 1.The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting through an image and duplicating adjacent pages to assure complete continuity. 2. When an image on the film is obliterated with a round black mark, it is an indication of either blurred copy because of movement during exposure, duplicate copy, or copyrighted materials that should not have been filmed.