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Masterarbeit MASTERARBEIT Titel der Masterarbeit „Synthesis of phosphonic acid analogues of 2-AEP and 1-OH-2-AEP as substrates for PhnY and PhnZ“ verfasst von Margret Vogt BSc angestrebter akademischer Grad Master of Science (MSc) Wien, 2015 Studienkennzahl lt. Studienblatt: A 066 862 Studienrichtung lt. Studienblatt: Masterstudium Chemie Betreut von: Ao. Univ.-Prof. Dr. Friedrich Hammerschmidt Wie Albert Einstein bereits sagte: Zwei Dinge sind zu unserer Arbeit nötig: Unermüdliche Ausdauer und die Bereitschaft, etwas, in das man viel Zeit und Arbeit gesteckt hat, wieder wegzuwerfen. Gib nie etwas auf, was du wirklich willst. Jemand mit großen Träumen ist mächtiger als jemand mit all den Fakten. Probleme kann man niemals mit derselben Denkweise lösen, durch die sie entstanden sind. Um ein tadelloses Mitglied einer Schafherde sein zu können, muss man vor allem ein Schaf sein. 5 6 1. Table of contents 1. Table of contents ............................................................................................................................. 7 2. Aim of Master thesis ...................................................................................................................... 10 3. Theoretical background ................................................................................................................. 12 3.1. Organophosphonates.............................................................................................................. 12 3.1.1. Biosynthesis of phosphonates ......................................................................................... 14 3.1.1.1. Decarboxylation ...................................................................................................................... 15 3.1.1.2. Condensation with acetyl-CoA ............................................................................................... 16 3.1.2. Biodegradation of phosphonates .................................................................................... 17 3.1.2.1. C-P lyase – microbial phosphonate catabolism under Pho-regulon control .......................... 18 3.1.2.2. C-P hydrolases – microbial phosphonate catabolism independent of Pho-regulon control . 22 3.1.2.3. PhnY and PhnZ – phosphonate catabolism by oxidative P-C cleavage .................................. 29 3.1.3. The contribution of organophosphonates to the global P cycle ..................................... 34 3.2. Phosphorus reactions.............................................................................................................. 35 3.2.1. Mitsunobu reaction ......................................................................................................... 35 3.2.2. Michaelis-Arbuzov reaction ............................................................................................. 36 3.2.3. Pudovik reaction .............................................................................................................. 37 3.2.4. Abramov reaction ............................................................................................................ 38 4. Results and discussion ................................................................................................................... 40 4.1. (2-(Methylamino)ethyl)phosphonic acid (2.3) ........................................................................ 40 4.2. (±)-(1-Hydroxy-2-(methylamino)ethyl)phosphonic acid [(±)-2.4] ........................................... 41 4.3. (±)-(1,2-Diaminoethyl)phosphonic acid [(±)-2.5] .................................................................... 43 4.4. (±)-(2-Amino-1-fluoroethyl)phosphonic acid [(±)-2.6] ............................................................ 45 4.5. (±)-Methyl hydrogen (2-amino-1-hydroxyethyl)phosphonate [(±)-2.7] ................................. 48 4.6. Methyl hydrogen (2-aminoethyl)phosphonate (2.8) .............................................................. 50 4.7. (3-Aminopropyl)phosphonic acid (2.9) ................................................................................... 52 4.8. (Aminooxymethyl)phosphonic acid (2.10) .............................................................................. 53 4.9. (Hydrazinomethyl)phosphonic acid (2.11) .............................................................................. 54 4.10. (R)- and (S)-(2-aminopropyl)phosphonic acid [(R)- and (S)-2.12] ......................................... 58 4.11. (3-Aminoprop-1-enyl)phosphonic acid (2.13) ...................................................................... 60 4.12. Final conclusions of the test results ...................................................................................... 62 5. Experimental part .......................................................................................................................... 63 7 5.1. General characterisation methods and determination of optical purity ............................... 63 5.2. General procedures ................................................................................................................ 63 5.3. Enzyme tests with PhnY and PhnZ .......................................................................................... 64 5.4. Synthesis of (2-(methylamino)ethyl)phosphonic acid (2.3) .................................................... 65 5.4.1. Diethyl (2-bromoethyl)phosphonate (4.1) ...................................................................... 65 5.4.2. (2-(Methylamino)ethyl)phosphonic acid (2.3) ................................................................. 65 5.5. Synthesis of (±)-(1-hydroxy-2-(methylamino)ethyl)phosphonic acid [(±)-2.4] ....................... 66 5.5.1. (±)-(Epoxyethyl)phosphonic acid, triethylammonium salt [(±)-4.2] ................................ 66 5.5.2. (±)-(1-Hydroxy-2-(methylamino)ethyl)phosphonic acid [(±)-2.4] .................................... 66 5.6. Synthesis of (±)-(1,2-diaminoethyl)phosphonic acid [(±)-2.5] ................................................ 67 5.6.1. N-(2-Hydroxyethyl)phthalimide (4.3) .............................................................................. 67 5.6.2. (2-Phthalimido)acetaldehyde (4.4) .................................................................................. 68 5.6.3. (±)-Diisopropyl (2-phthalimido-1-(trimethylsiloxy)ethyl)phosphonate [(±)-4.6] ............ 68 5.6.3.1. Diisopropyl trimethylsilyl phosphite (4.5) .............................................................................. 69 5.6.4. (±)-Diisopropyl (1-hydroxy-2-phthalimidoethyl)phosphonate [(±)-4.7] .......................... 70 5.6.5. (±)-Diisopropyl (1-azido-2-phthalimidoethyl)phosphonate [(±)-4.8] .............................. 70 5.6.6. (±)-(1,2-Diaminoethyl)phosphonic acid [(±)-2.5] ............................................................. 71 5.7. Synthesis of (±)-(2-amino-1-fluoroethyl)phosphonic acid [(±)-2.6] ........................................ 72 5.7.1. (±)-Diethyl 2-fluoro-2-phosphonoacetamide [(±)-4.15] .................................................. 72 5.7.2. (±)-Diethyl (2-amino-1-fluoroethyl)phosphonate [(±)-4.16] ........................................... 73 5.7.3. (±)-(2-Amino-1-fluoroethyl)phosphonic acid [(±)-2.6] ..................................................... 73 5.8. Synthesis of (±)-methyl hydrogen (2-amino-1-hydroxyethyl)phosphonate [(±)-2.7] ............. 74 5.8.1. (±)-Dimethyl (1-hydroxy-2-phthalimidoethyl)phosphonate [(±)-4.18]............................ 74 5.8.2. (±)-Methyl hydrogen (2-amino-1-hydroxyethyl)phosphonate [(±)-2.7] .......................... 75 5.9. Synthesis of methyl hydrogen (2-aminoethyl)phosphonate (2.8) .......................................... 76 5.9.1. N-(2-Bromoethyl)phthalimide (4.23) ............................................................................... 76 5.9.2. Dimethyl (2-phthalimidoethyl)phosphonate (4.24) ........................................................ 76 5.9.3. Methyl hydrogen (2-aminoethyl)phosphonate (2.8) ....................................................... 77 5.10. Synthesis of (3-aminopropyl)phosphonic acid (2.9) ............................................................. 78 5.10.1. N-(3-Bromopropyl)phthalimide (4.25) ........................................................................... 78 5.10.2. Diethyl (3-phthalimidopropyl)phosphonate (4.26) ....................................................... 79 5.10.3. (3-Aminopropyl)phosphonic acid (2.9) .......................................................................... 79 5.11. Synthesis of (aminooxymethyl)phosphonic acid (2.10) ........................................................ 80 8 5.11.1. Diisopropyl (hydroxymethyl)phosphonate (4.27) ......................................................... 80 5.11.2. Diisopropyl (1-phthalimidooxymethyl)phosphonate (4.28) .......................................... 81 5.11.3. (Aminooxymethyl)phosphonic acid (2.10) ..................................................................... 81 5.12. Synthesis of (hydrazinomethyl)phosphonic acid (2.11)........................................................ 82 5.12.1. Diisopropyl (bromomethyl)phosphonate (4.29) ............................................................ 82 5.12.2. Diethyl (hydroxymethyl)phosphonate (4.34) ................................................................ 83 5.12.3. Diethyl (mesyloxymethyl)phosphonate (4.35) .............................................................. 83 5.12.4. Diethyl (N,N‘-di-Boc-hydrazinomethyl)phosphonate (4.37) ........................................
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