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Investigation of a Metal Complexing Route to Arene Trans-Dihydrodiols

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Investigation of a Metal Complexing Route to Arene Trans-Dihydrodiols Technological University Dublin ARROW@TU Dublin Masters Science 2010-01-01 Investigation of a Metal Complexing Route to Arene Trans- Dihydrodiols Crystal O'Connor Technological University Dublin Follow this and additional works at: https://arrow.tudublin.ie/scienmas Part of the Other Pharmacy and Pharmaceutical Sciences Commons Recommended Citation O'Connor, C. (2010). Investigation of a Metal Complexing Route to Arene Trans-Dihydrodiols. Masters dissertation. Technological University Dublin. doi:10.21427/D77P55 This Theses, Masters is brought to you for free and open access by the Science at ARROW@TU Dublin. It has been accepted for inclusion in Masters by an authorized administrator of ARROW@TU Dublin. For more information, please contact [email protected], [email protected]. This work is licensed under a Creative Commons Attribution-Noncommercial-Share Alike 4.0 License Investigation of a Metal Complexing Route to Arene trans-Dihydrodiols By Crystal O'Connor B.Sc. (Hons.) A Thesis submitted to the Dublin Institute of Technology for the Degree of MPhil Supervised by Dr. Claire McDonnell (DIT) and Prof. Rory More O’Ferrall (UCD) School of Chemical and Pharmaceutical Sciences Dublin Institute of Technology Kevin Street, Dublin 8. July 2010 For Mum and Dad I "Nothing shocks me, I'm a Scientist." Indiana Jones (Indiana Jones and the Temple of Doom) II Abstract In this work, a route for the conversion of arene cis-dihydrodiols to their trans isomers was examined. Arene trans-dihydrodiols are potentially important chiral building blocks in synthetic chemistry and are more stable than their cis analogues. While the cis-arene dihydrodiols can be produced on a relatively large scale by fermentation, their trans isomers cannot. The principal aim of this work was to carry out studies in tandem to inform the development of the synthetic pathway to convert arene cis-dihydrodiols to their trans isomers by (a) the synthesis of organometallic intermediates and (b) investigation of their reactivity by means of kinetic and equilibrium studies. A number of analogues based on seven- membered ring systems instead of six were also investigated as a comparison. The four-step synthetic route being investigated involved formation of a tricarbonyl iron complex of the arene cis-dihydrodiol substrate, followed by reaction in acid to form a carbocation intermediate. This cation complex is trapped stereoselectively using hydroxide to give a trans isomer and decomplexation to remove the iron tricarbonyl moiety is the final step. Two substrates were examined, 3- bromocyclohexa-3,5-diene-1,2-diol and 3-trifluoromethylcyclohexa-3,5-diene-1,2- diol. The first three steps in the route were successfully performed on each compound in yields of 52 % and 43 % overall for the 3-bromo and 3-trifluoromethyl starting materials respectively. The final decomplexation step was not successful however and will require optimisation of the conditions. The ionisation of the tricarbonyl iron cis-dihydrodiol intermediates was investigated kinetically in strong acid, and the corresponding rate constant for the bromo substituted complex was determined to be 8.0 x 10-8 M-1 s-1 showing a significant lack of reactivity towards cation complex formation. This is expected based on previous work that reports low reactivity towards ionisation for any complexes that have hydroxyl groups endo to the iron centre, as is the case here. The reverse reaction, hydrolysis of the bromo-substituted cation, was too fast to measure but a pKR of 0.5 was estimated. III It can be concluded that ionisation of the coordinated endo (i.e. cis-) diol to form the corresponding cation is the difficult step in the route to convert arene cis- dihydrodiols to their trans isomers. Among the seven-membered ring complexes synthesised were salts of the cation species, tricarbonyl (η5-cyclohepta-1,3-dienyl) iron and tricarbonyl (η7- cycloheptatrienyl) chromium. Rate constants for the nucleophilic reaction of the former cation complex with water to give tricarbonyl (η5-cyclohepta-2,4-diene-1-ol iron) and conversion of this complex back to the cation were measured, allowing a pH profile (log k versus pH) to be constructed. From this, an equilibrium constant, pKR, = 4.2 was determined for the interconversion between the cycloheptadienyl complex [R+] and the corresponding hydrolysis product [ROH] in which the hydroxyl group is exo to the iron centre. Comparison of this equilibrium constant to that reported for the uncoordinated cycloheptadienyl cation shows that the iron tricarbonyl moiety is highly stabilising (∆pKR = 15.8). The uncoordinated tropylium (or cycloheptatrienyl) ion however shows a similar stability to tricarbonyl (η5-cyclohepta-1,3-dienyl) iron due to aromatic stabilisation. The effect of having one less methylene group in the ring was found to be negligible as ∆p KR = 0.4 for the coordinated cycloheptadienyl and cyclohexadienyl cations. It is proposed that, in weak base, the tricarbonyl cycloheptatrienyl chromium complex gives a zwitterionic complex in which a carbonyl ligand is converted to a carboxylate ion. Equilibrium between this zwitterion and a cationic form in which the carboxylate has been protonated to give the carboxylic acid is postulated to occur in weakly acid solutions. An acid dissociation constant, pKa of 4.8 was determined for this equilibrium spectrophotometrically. IV Declaration I certify that this thesis which I now submit for the award of an MPhil is entirely my own work and has not been taken from the work of others save and to the extent that such work has been cited and acknowledged within the text of my own work. This thesis was prepared according to the Regulations for Postgraduate Study by Research of the Dublin Institute of Technology and has not been submitted in whole or in part for an award of any other Institute or University. The work reported on in this thesis conforms to the principles and requirements of the Institute's guidelines for ethics in research. The Institute has permission to keep, to lend or to copy this thesis in whole or in part, on condition that any such use of the material of the thesis be duly acknowledged. Signature______________________ Date_______________ Candidate V Acknowledgements I would first like to thank my supervisors Dr. Claire McDonnell and Prof. Rory More O'Ferrall for all their help and guidance throughout my studies. Their time and effort is very much appreciated. I would like to give a special thanks to those in the MSA lab. Thanks to Catriona for her help with starting this project; to the great Miriam for being deadly and proof reeding everything (she wrote that bit herself); Nick, my office "neighbour"; Gary (let's consult the iPhone); Damian (Mac-Man) and Mark (the chumpmeister). Also thank you to Aoife, the great procrastinator, who kept me entertained in the lab in the mornings; and to Anne for making the bus journey pass quicker. Thank you all for your friendship over the years and I wish you all luck for the future. A huge thanks to my best friends Aoife and Krystle who have supported me over the past 15 years and hopefully will never mention the word thesis again under threat of torture. Finally, I would like to give the biggest thanks to my family, especially to my parents for all their encouragement. To my brothers and sister, and to my nieces and nephews, especially Ryan who always acted interested when his Auntie Crystal started talking about that science stuff. VI Table of Contents Abstract iii Declaration v Acknowledgements vi Table of Contents vii Table of Figures xiv Table of Tables xviii Abbreviations xxii CHAPTER 1 INTRODUCTION. ............................................................................... 1 1.1 OXIDATIVE METABOLITES OF AROMATIC HYDROCARBONS. ................................... 1 1.1.1 ARENE CIS- AND TRANS-DIHYDRODIOLS. .......................................................... 4 1.2 ORGANOMETALLIC CHEMISTRY. .......................................................................... 7 1.2.1 ORGANOIRON CHEMISTRY. ............................................................................... 7 1.2.1.1 Initial Synthesis of Tricarbonyl Iron Complexes. ......................................... 8 1.2.2 TRICARBONYL IRON COMPLEXATION USING TRICARBONYL IRON TRANSFER REAGENTS. .............................................................................................................. 10 1.2.2.1 Grevels’ Reagent. ..................................................................................... 11 1.2.2.2 1-Azabuta-1,3-dienes................................................................................ 12 1.2.3 SYNTHETIC APPLICATIONS OF TRICARBONYL IRON COMPLEXES. ........................ 14 1.2.3.1 The Tricarbonyl Iron Fragment as a Protecting Group. ............................. 14 1.2.3.2 Stereochemical Control Using the Tricarbonyl Iron Group. ........................ 15 1.2.3.3 Tricarbonyl Iron as an Activating Group. .................................................... 16 1.2.3.4 Stabilising Ability of the Tricarbonyl Iron Unit. ............................................ 16 1.2.3.5 Tricarbonyl Cyclohexadienyl Iron Complexes. ........................................... 16 1.2.3.6 Synthetic Applications of Tricarbonyl Cyclohexadienyl Iron Complexes. ... 18 1.2.3.7 Ligand Exchange of a Carbonyl Ligand for a Triphenylphosphine Ligand……….. ....................................................................................................... 19 VII 1.2.3.8 Decomplexation of Tricarbonyliron
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