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Synthesis and Characterisation of MOP-Phosphonite Complexes and Their Applications in Asymmetric Catalysis

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Synthesis and Characterisation of MOP-Phosphonite Complexes and Their Applications in Asymmetric Catalysis Synthesis and Characterisation of MOP-phosphonite Complexes and their Applications in Asymmetric Catalysis PhD Thesis Submitted by James T. Fleming Supervisor: Dr Lee J. Higham School of Chemistry Faculty of Science, Agriculture and Engineering Newcastle University Newcastle upon Tyne United Kingdom Abstract In this thesis we report our synthesis of user-friendly, chiral phosphonite ligands, based upon Hayashi’s MOP backbone, and their application in asymmetric catalytic transformations. Chapter 1 gives an introduction to organophosphorus ligands in catalysis and the use of air-stable primary phosphines as precursors in the synthesis of functionalised phosphorus compounds. Chapter 2 details our synthesis and characterisation of the enantiopure MOP-phosphonite ligands (S)-28a and (R)-28b containing two phenoxy substituents, (S)-29a and (R)-29b with a biphenoxy moiety and (S)-30a and (R)-30b with a 3,3'-dimethylbiphenoxy group. These ligands are proven to be very successful in high-yielding, regio- and enantioselective palladium-catalysed hydrosilylation reactions of substituted styrenes, affording important chiral secondary alcohols, with (S)-30a achieving ees of up to 95%. In-depth NMR studies reveal the hemilabile nature of the bonding of (R)-30a in a palladium 2-methylallyl complex, where the phosphonite ligand acts as a chelating P,C-π-donor. In Chapter 3 we compare our series of novel ligands via experimental and computational methods in an effort to quantify their differing structural and electronic profiles. Four [Rh(LP)(η2:η2-cod)Cl] and two P [Rh(L )2]BF4 complexes were synthesised and characterised by NMR spectroscopy, HRMS and, in all but one case, by X-ray crystallography. Rh() complexes were used as catalysts in industrially relevant asymmetric hydrogenation and hydroformylation reactions. Pd() complexes were successfully employed in asymmetric Suzuki-Miyaura cross-coupling reactions yielding binaphthyl products and P two of the [Pd(L )2Cl2] catalysts were isolated and characterised by X-ray crystallography. The final chapter details the preparation of copper, silver and gold complexes of our P MOP-phosphonites. Six [Au(L )Cl] complexes were prepared as was the complex [Au((S)-30a)2]SbF6. Six P P [Ag(L )OTf] complexes were synthesised, as were six [Cu(L )(MeCN)2]PF6 complexes. Extensive NMR and X-ray crystallographic analyses undertaken on these compounds reveals that any M–π interactions appear weak, if present at all. I Acknowledgements I would like to thank my supervisor Dr Lee Higham for his support and guidance during my PhD. I have had the opportunity to learn many different skills throughout my time in his research group, with interesting and varied projects, and have been given a great deal of freedom to pursue my own ideas and interests. Specifically thank you for sending me to numerous conferences and summer schools, I greatly appreciate every opportunity and I enjoyed them all. My second supervisor Dr Michael Hall has also always given helpful advice, alongside a few pints of beer, and I very much appreciate the conversations we have had over the years. My time in the lab was made enjoyable and memorable by many people. Notably, Dr Manuel Abelairas-Edesa, Dr Arne Ficks and Dr Connor Sibbald who taught me most of what I know and have become great friends hopefully our annual holiday will continue for many years! I have also had unforgettable times with Jennifer Wallis and Antonio Sanchez-Cid, thank you for keeping me cheerful as I wrote multiple papers and a thesis during the cold winter months. To complete the LJH research group I must thank Dr Laura Davies, Dr Ana Cioran, Graeme Bowling and Charlotte Hepples. Dr Thomas Winstanley deserves a special mention as an honorary LJH alumnus. I have also made many friends over the years with MChem, Erasmus and summer students who have passed through the lab in particular Giorgia Fagnani and Bebhinn Tully-Penon. I must thank the school of chemistry for funding my PhD and all members of the department who have made this work possible through their hard work and helpful support. With specific regards to my research: NMR Dr Corinne Wills and Prof. William McFarlane; X-ray Dr Paul Waddell, Dr Ross Harrington, Dr Michael Probert and Prof. William Clegg; Computing Dr Jerry Hagon. A special thank you to my parents, family and Hannah who have always been so enthusiastic and supportive about my academic adventures. I have always placed far more pressure upon myself to succeed than anyone else has, so thank you for keeping me calm and grounded. II List of Publications I. N. Fey, S. Papadouli, P. G. Pringle, A. Ficks, J. T. Fleming, L. J. Higham, J. F. Wallis, D. Carmichael, N. Mézailles and C. Müller, Setting P-Donor Ligands into Context: An Application of the Ligand Knowledge Base (LKB) Approach, Phosphorus Sulfur Silicon Relat. Elem., 2014, 190, 706. II. J. T. Fleming and L. J. Higham, Primary phosphine chemistry, Coord. Chem. Rev., 2015, 297–298, 127. III. J. T. Fleming, A. Ficks, P. G. Waddell, R. W. Harrington and L. J. Higham, The design of second generation MOP-phosphonites: efficient chiral hydrosilylation of functionalised styrenes, Dalton Trans., 2016, 45, 1886. IV. J. T. Fleming, C. Wills, P. G. Waddell, R. W. Harrington and L. J. Higham, A comparison of MOP-phosphonite ligands and their applications in Rh()- and Pd()-catalysed asymmetric transformations, Dalton Trans., 2016, 45, 15660. III Abbreviations General aq. Aqueous solution L Arbitrary ligand R Arbitrary organic substituent LP Arbitrary phosphorus ligand Ar Aryl AHF Asymmetric hydroformylation AH Asymmetric hydrogenation AHS Asymmetric hydrosilylation AM1 Austin model one B3LYP Becke, three-parameter, Lee-Yang-Parr Bn Benzyl Bu Butyl Cy Cyclohexyl DFT Density functional theory de Diastereomeric excess ee Enantiomeric excess Et Ethyl GC Gas chromatography ΔG Gibbs free energy η Hapticity HOMO Highest occupied molecular orbital HPLC High-performance liquid chromatography θ Ligand cone angle LKB Ligand knowledge base LUMO Lowest unoccupied molecular orbital MP Melting point Me Methyl Ph Phenyl Pr Propyl Rf Retention factor SOMO Singly occupied molecular orbital IV ퟐퟎ [휶]푫 Specific Rotation (20 °C, D = Wavelength of the sodium D line (589 nm)) S4' Symmetric deformation coordinate BArF Tetrakis[3,5-bis(trifluoromethyl)phenyl]borate TLC Thin-layer chromatography TM Transition metal TS Transition state Tf / Triflate Trifluoromethanesulfonyl Trip 2,4,6-Triisopropylphenyl Mes 2,4,6-Trimethylphenyl TMS Trimethylsilyl Mes* 2,4,6-Tri-tert-butylphenyl 2D Two-dimensional UV Ultraviolet UV-Vis Ultraviolet-visible Chemicals acac Acetylacetone SEGPHOS 4,4'-Bi-1,3-benzodioxole-5,5'-diylbis(diphenylphosphine) H-MOP ([1,1'-Binaphthalen]-2-yl)diphenylphosphine BINOL 1,1'-Bi-2-naphthol BINAP 2,2'-Bis(diphenylphosphino)-1,1'-binaphthalene DPPP 1,3-Bis(diphenylphosphino)propane COD 1,5-Cyclooctadiene DCE Dichloroethane DCM Dichloromethane DIPEA N,N-Diisopropylethylamine MeO-BIPHEP 6,6'-Dimethoxy-2,2'-bis(diphenylphosphino)-1,1'-biphenyl BIPHEMP 6,6'-Dimethyl-2,2'-bis(diphenylphosphino)-1,1'-biphenyl DMI Dimethyl itaconate DMSO Dimethyl sulfoxide HO-MOP (2'-Hydroxy-[1,1'-binaphthalen]-2-yl)diphenylphosphine DIOP 2,3-o-Isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane MeO-MOP (2'-Methoxy-[1,1'-binaphthalen]-2-yl)diphenylphosphine PMB p-Methoxybenzyl V MAA Methyl 2-acetamidoacrylate MAC Methyl (Z)-2-acetamidocinnamate KenPhos (2'-Dimethylamino-[1,1'-binaphthalen]-2-yl)dicyclohexylphosphine CAMP Methylcycohexyl-o-anisylphosphine PAMP Methylphenyl-o-anisylphosphine Ph-MOP (2'-Phenyl-[1,1'-binaphthalen]-2-yl)diphenylphosphine TADDOL α,α,α',α'-Tetraaryl-1,3-dioxolane-4,5-dimethanol THF Tetrahydrofuran tht Tetrahydrothiophene TMEDA N,N,N',N'-Tetramethylethylenediamine Infrared (IR) Spectroscopy FT Fourier transform Frequency m Medium s Strong w Weak Mass Spectrometry ASAP Atmospheric-pressure solids analysis probe HRMS High-resolution mass spectrometry LRMS Low-resolution mass spectrometry MALDI Matrix-assisted laser desorption ionisation NSI Nanospray ionisation Nuclear Magnetic Resonance (NMR) Spectroscopy br Broad δ Chemical shift COSY Correlation spectroscopy J Coupling constant d Doublet EXSY Exchange spectroscopy HSQC Heteronuclear single quantum correlation HMBC Heteronuclear multiple-bond correlation m Multiplet VI NOE Nuclear Overhauser effect NOESY Nuclear Overhauser effect spectroscopy I Quantum spin number q Quartet ROE Rotating frame Overhauser effect ROESY Rotating frame Overhauser effect spectroscopy s Singlet t Triplet VT Variable temperature Units Å Ångström cm Centimetre ° Degree oC Degrees Celsius eV Electron volt eq. Equivalent g Grams Hz Hertz h Hour K Kelvin MHz MegaHertz μmol Micromoles mg Milligram mL Millilitre mm Millimetre mmol Millimoles ms Millisecond min Minute M Molar concentration ppm Parts per million VII Table of Contents Abstract .................................................................................................................................................... I Acknowledgements ................................................................................................................................. II List of Publications ................................................................................................................................. III Abbreviations ........................................................................................................................................ IV Table of Contents ...............................................................................................................................
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