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1

Coetzee, Karolien. "Gold complexes obtained from gold ylide preparations." Thesis, Stellenbosch : Stellenbosch University, 2005. http://hdl.handle.net/10019.1/21206.

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Thesis (MSc)--University of Stellenbosch, 2005.
ENGLISH ABSTRACT: This investigation comprised the synthesis and characterisation of new Au(I) phosphonium ylide complexes and other compounds formed during coordination reactions. These complexes could exploit the synergism between two pharmacologically active substances (gold complex unit and phosphorus ylide) to furnish an even more active substance. Four phosphonium salts were prepared, [C6H5CH2PPh3]Br (1), [Ph3P(CH2)3PPh3]Br2 (2a), p-[{Ph3PCH2}2C6H4]Br2 (3a) and m- [{Ph3PCH2}2C6H4]Br2 (4a), by reacting PPh3 with the corresponding alkylbromides. The 13C and 1H NMR spectra of the compounds 1 – 4a indicated that many of the nuclei are magnetically inequivalent. The aromatic units in PPh3 are normally identical, but multiple, overlapping signals proved that the corresponding ortho, meta and para carbon and proton nuclei are in magnetically different environments from each other. Single crystal structures of salts 3a and 4a were determined. Different methods were followed to deprotonate the phosphonium salts to afford the corresponding ylides and to coordinate the ylides to gold precursor compounds. Most of the reactions yielded inseparable mixtures of products and pure compounds could not be isolated in large enough quantities for characterisation by all physical methods. Sufficient crystals for structure determination by X-ray diffraction were obtained. The product mixtures were characterised by 1H, 13C and 31P NMR spectroscopy and mass spectrometry. Characteristic downfield chemical shift changes after coordination of the ylides to Au(I) were observed for the carbon and phosphorus nuclei, while the protons displayed upfield shifts. Reaction of (C6F5)Au(tht) with the salts 1 – 4a, and subsequent deprotonation yielded the gold(I) ylide complexes [C6H5CH(AuC6F5)PPh3] (5), [{Ph3PCH(AuC6F5)}2CH2] (6), p-[{Ph3PCH(AuC6F5)}2C6H4] (8), and m- [{Ph3PCH(AuC6F5)}2C6H4] (9). The crystal and molecular structures of compounds 5 and 9 were determined. Deprotonation of 4a with n-BuLi, followed by reaction with (C6F5)Au(tht) yielded complexes 9 and [{Ph3PCH2}2C6H4][BrAuC6F5]2 (10). The crystal structure of compound 10 was determined. Two aurocyclic compounds, [μ- {(Ph3PCH)2CH2}2Au2][BF4]2 (12) and [μ–{(Ph3PCH)2C6H4}2Au2][BF4]2 (13) were synthesised by deprotonating salts 2b and 3b with n-BuLi and subsequently reacting the corresponding bisylides with ClAu(tht). Reaction procedures in which Ag2O was used as deprotonating agent for the phosphonium salts 2a, 3a and 4a, yielded mixtures of products. Single crystals of complexes m-[Ph3PCH(AuC6F5)C6H4CH3] (14), [C6F5Au(tht)] (15) and [(C6F5)2Au][(Ph3PCH2)2C6H4] (16) were isolated from the reaction mixtures and subjected to X-ray crystal structure determination. The molecular structure of 15 exhibited unusual aurophilic interactions and represents the first example of a linear gold chain in which the gold···gold distances systematically alternate between 3.13Å, 3.31Å and 3.20Å. Salt 2b was reacted with Ph3PAu(acac) to afford the desired compound, [{Ph3PCH(AuPPh3)}2CH2](BF4)2 (19), along with [CH3C(O)C(AuPPh3)2C(O)CH3] (17) and some byproducts. Compound 17 was characterised by single crystal Xray diffraction. The fluorobiphenylgold(I) complexes, 4,4’-[(AuPPh3)2C12F8] (21) and 2,2’- [(AuPPh3)2C12F8] (22) were synthesised by reaction of ClAuPPh3 with the lithiated 2,2’-dibromooctafluorobiphenyl and 4,4’-dibromooctafluorobiphenyl respectively. The molecular structure of 21 revealed that one of the C–Au–P bond angles deviates from linearity by 12.5°, probably as a result of π-stacking of the tetrafluorophenyl rings and steric requirements of the bulky PPh3 units. The other C–Au–P bond angle is linear [177.9(3)°].
AFRIKAANSE OPSOMMING: Hierdie studie behels die sintese en karakterisering van nuwe fosfoniumylied goud(I)-komplekse en ander verbindings wat gedurende koördinasiereaksies vorm. Sulke komplekse kan sinergisme tussen twee farmakologies-aktiewe entiteite (goud(I) en fosfoniumylied) om ʼn meer aktiewe verbinding te vorm meebring. Vier fosfoniumsoute is berei, [C6H5CH2PPh3]Br (1), [Ph3P(CH2)3PPh3]Br2 (2a), p- [{Ph3PCH2}2C6H4]Br2 (3a) en m-[{Ph3PCH2}2C6H4]Br2 (4a), deur PPh3 met die ooreenstemmende alkielbromiedes te reageer. Die 13C- en 1H- KMR-spektra van dié verbindings toon dat ʼn aantal kerne in aromatiese ringe magneties onekwivalent is. Normaalweg is die koolstowwe in PPh3-eenhede ekwivalent, maar meervoudige, oorvleuelende pieke het nou getoon dat die ooreenstemmende orto-, meta- en para-koolstof sowel as die ooreenstemmende protonkerne in verskillende magnetiese omgewings voorkom. Die kristalstrukture van die soute 3a en 4a hierbo is met behulp van X-straal tegnieke bepaal. Verskillende metodes is gevolg om die fosfoniumsoute te deprotoneer na die ooreenstemmende yliede en om die yliede dan aan goud-bevattende uitgangstowwe te probeer koördineer. Die meeste reaksies het nie-skeibare mengsels gevorm en enkelprodukte kon nie in groot genoeg konsentrasies geïsoleer word om hulle afsonderlik te karakteriseer nie. Kristalle vir X-straal kristalstruktuur bepalings is verkry. Die produkmengsels is gekarakteriseer met behulp van 1H-, 13C- en 31P- KMR-spektroskopie en massaspektrometrie. Karakteristieke veranderinge in chemiese verskuiwings na laer veldsterktes vir die koolstof en fosfor kerne is waargeneem na koördinasie van die yliede aan Au(I), terwyl die protone na höer veldsterktes verskuif het. Die reaksie tussen (C6F5)Au(tht) (tetrahidrotiofeen) en soute 1 – 4a gevolg deur deprotonering, vorm die goud-yliedkomplekse [C6H5CH(AuC6F5)PPh3] (5), [{Ph3PCH(AuC6F5)}2CH2] (6), p-[{Ph3PCH(AuC6F5)}2C6H4] (8), en m- [{Ph3PCH(AuC6F5)}2C6H4] (9). Die kristalstrukture van komplekse 5 en 9 het al die molekulêre interaksies daarin blootgelê. Deprotonering van 4a met n-BuLi, gevolg deur reaksie met (C6F5)Au(tht) lewer komplekse 9 en [{Ph3PCH2}2C6H4][BrAuC6F5]2 (10). Die kristal- en molekulêre struktuuur van kompleks 10 is bepaal. Twee aurosikliese verbindings, [μ- {(Ph3PCH)2CH2}2Au2][BF4]2 (12) en [μ–{(Ph3PCH)2C6H4}2Au2][BF4]2 (13) is gesintetiseer deur gedeprotoneerde bisyliede verkry van 2b en 3b met substitusie van tht aan die ClAu-eenheid te koördineer. Reaksieprosedures waarin Ag2O vir deprotonering van die fosfoniumsoute 2a, 3a en 4a gebruik is, het tot mengsels van produkte aanleiding gegee. Enkelkristalle van komplekse [Ph3PCH(AuC6F5)C6H4CH3] (14), [C6F5Au(tht)] (15) en [(C6F5)2Au][(Ph3PCH2)2C6H4] (16) is geïsoleer uit die reaksies en kristalstruktuurbepalings is uitgevoer. Die molekulere struktuur van 15 toon ongewone aurofiliese interaksies en verteenwoordig die eerste voorbeeld van ʼn linieêre goudketting; met goud···goud afstande wat sistematies varieër tussen 3.13Å, 3.31Å en 3.20Å. Sout 2b is met Ph3PAu(acac) gereageer om die gewenste produk, [{Ph3PCH(AuPPh3)}2CH2](BF4)2 (19), saam met [CH3C(O)C(AuPPh3)2C(O)CH3] (17) en ander byprodukte te vorm. Verbinding 17 is as enkelkristalle Xstraalkristallografies gekarakteriseer. Die fluorobifeniel goud(I)-komplekse, 4,4’-[(AuPPh3)2C12F8] (21) en 2,2’- [(AuPPh3)2C12F8] (22), is gesintetiseer deur koördinasie van AuPPh3 aan die gelitieërde 2,2’-dibromooktafluorobifeniel en 4,4’-dibromooktafluorobifeniel respektiewelik. Die molekulere struktuur van 21 het getoon dat een van die C-Au- P bindingshoeke met 12.5º afwyk van 180º, waarskynlik as gevolg van π- interaksie van die tetrafluorofenielringe en die steriese vereistes van die groot PPh3-eenhede. Die ander C-Au-P bindingshoek is linieêr [177.9(3)°].
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2

Yang, Yi. "Gold(I) oxo, imido, hydrazido complexes and gold clusters /." free to MU campus, to others for purchase, 1996. http://wwwlib.umi.com/cr/mo/fullcit?p9841362.

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3

Coetzee, Jacorien. "New developments in the coordination chemistry of gold(1), gold(II) and gold(III) with C-, N-, P-and S-Donor ligands /." Link to the online version, 2007. http://hdl.handle.net/10019/412.

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4

Yau, John. "The chemistry of gold(I) compounds." Thesis, Imperial College London, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.338901.

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5

Haggitt, Jane Louise. "Cluster compounds of platinum and gold." Thesis, University of Oxford, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.334859.

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6

Elsome, Amanda Maria. "Some biological interactions of gold compounds." Thesis, King's College London (University of London), 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.283198.

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7

LeBlanc, Daren James. "Thiol complexes of gold(I) : structure and chemistry of the gold based anti-arthritis drugs /." *McMaster only, 1996.

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8

Chiffey, Andrew Francis. "Bimetallic compounds of palladium, platinum and gold." Thesis, University of Southampton, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.294602.

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9

肖紅 and Hong Xiao. "Photochemical, photophysical properties and structures of polynuclear gold(I) clusters and organometallic gold(I) complexes." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1996. http://hub.hku.hk/bib/B31235438.

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10

Xiao, Hong. "Photochemical, photophysical properties and structures of polynuclear gold(I) clusters and organometallic gold(I) complexes /." Hong Kong : University of Hong Kong, 1996. http://sunzi.lib.hku.hk/hkuto/record.jsp?B19669471.

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11

Coetzee, Jacorien. "New developments in the coordination chemistry of Gold(I), Gold(II) and Gold(III) with C-, N- , P-and S-donor ligands." Thesis, Stellenbosch : University of Stellenbosch, 2007. http://hdl.handle.net/10019.1/1702.

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Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2007.
A comprehensive, comparative structural study of gold(I), gold(II) and gold(III) compounds with the general formula [Aux(C6F5)y(tht)z] (tht = tetrahydrothiophene) was performed. The series of compounds included the unprecedented dinucleur gold(II) compound, tetrakis(pentafluorophenyl)bis(tetrahydrothiophene)digold(II), which could be prepared in a rational manner. This very unique compound represents the first example of an unbridged dinucleur gold(II) compound in which the gold(II) centres are not stabilised by chelating ligands. Formation of this compound was postulated to have taken place by radical pentafluorophenyl (pfp) ligand migration along with AuII–AuII bond formation. It may therefore be regarded as a rare example of labile behaviour by a generally inert pfp ligand. In addition to this compound, the crystal and molecular structures of the wellknown gold(I) and gold(III) precursor compounds, (pentafluorophenyl)(tetrahydrothiophene) gold(I) and tris(pentafluorophenyl)(tetrahydrothiophene)gold(III) were carried out and are described for the first time. The latter underwent a unique mononuclear ligand rearrangement (metathesis or disproportionation) reaction in solution to yield the novel rearrangement product, bis(pentafluorophenyl)bis(tetrahydrothiophene)gold(III)tetrakis- (pentafluorophenyl)gold(III). In all the complexes, the Au–C and Au–S bond lengths displayed a variation which appears to be dependent on the oxidation state of the central gold atom. Both of these bond types were found to descrease in the order Au(II) > Au(III) > Au(I)...
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12

Watson, Michael John. "Cluster compounds of gold and the platinum metals." Thesis, University of Oxford, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.279996.

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13

Asikainen, Martta Irmeli. "Synthesis and gold-catalyzed transformations of allenic compounds." Thesis, University of Nottingham, 2012. http://eprints.nottingham.ac.uk/12367/.

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This thesis is concerned with the synthesis of allenic compounds and their gold-catalyzed isomerization reactions. Its general aim is the development of new reaction methodologies within these topics and the work has been published in two separate articles. After an introductory chapter (covering relevant literature upto 2010) three separate projects are discussed: 1. Development of tandem enzyme/gold-catalyzed reaction where lipase-catalyzed kinetic resolution of alpha-allenic acetates [R1 2CCCH(CHR2OAc)] (R1,R2 = alkyl) leads to the formation of alpha-hydroxyallenes with 86-99% ee and this transformation is followed by the cycloisomerization of the alpha-hydroxyallenes to the corresponding 2,5-dihydrofurans in a one-pot reaction. It is found that the two transformations work well in one pot except in the case where R2 is branched, which are not hydrolysed. 2. A new approach is developed for the synthesis of allenyl acetates [Ar(R1)CCCH(O2CR2)] (R1 = alkyl, R2 = Me, Ph, t-Bu) using cuprate-mediated SN2’nucleophilic substitution to propargylic dicarboxylates. The reaction was successfull with a range of substrates (11 examples). Investigation on a catalytic variant for the synthesis of the above allenyl acetates. Nickel-catalyzed SN2’ nucleophilic substitution to propargylic dicarboxylates gives the highest selectivity of the desired allenic products but the transformation is not very high-yielding. Attempts towards an asymmetric reaction are thwarted by low enantioselectivities (<22% ee). 3. Comparing the reactivity of propargylic acetates and allenyl acetates (prepared in Sections 2-3) in the gold-catalyzed synthesis of indenes. It was discovered that the allenyl acetates prepared earlier yield indenes with up to quantitative yields and high chemoselectivity, whereas propargylic acetates with terminal a alkyne group only yielded a mixture of cyclization and elimination products.
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14

Fonteh, Pascaline Nanga. "Gold compounds with anti-HIV and immunomodulatory activity." Thesis, University of Pretoria, 2011. http://hdl.handle.net/2263/24951.

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The human immunodeficiency virus (HIV) and acquired immune deficiency syndrome (AIDS) that subsequently develops remain major health concerns even after three decades since the first cases were reported. Successful therapeutic measures to address HIV/AIDS consist mostly of combinations of drugs targeting viral enzymes including reverse transcriptase (RT), protease (PR) and integrase (IN) as well as entry steps of the viral life cycle. The remarkable benefits (e.g. improved quality of life) derived from the use of these agents are unfortunately limited by toxicity to the host and the development of drug resistant viral strains. Drug resistance limits the repertoire of drug combinations available. Unfortunately, because latent forms of the virus exists, therapy has to be life-long and with new infections occurring every day, resistant strains tend to spread. To circumvent these problems, new drugs that inhibit resistant strains or work against new viral targets have to be developed. The history of gold compounds as potential inhibitors of HIV prompted this study in which twenty seven compounds consisting of gold(I), gold(III) and precursors from five classes were tested for drug-likeness, anti-HIV and immunomodulatory effects using wet lab and in silico methodologies. Cytotoxicity determination was done using viability dyes and flow cytometry. Cell proliferation profiles were monitored using the carboxyflourescein succinimidyl ester dye dilution technology and a real time cell analyser for confirming viability dye findings. The compounds’ effects on viral enzymes was determined using direct enzyme assays and in silico molecular modelling techniques. H and P nuclear magnetic resonance spectroscopy studies for determining stability revealed that the backbone chemical shifts of the compounds were relatively unchanged after one week (-20 and 37 ºC) when dissolved in dimethylsulfoxide. Eight of the gold compounds had drug-like properties comparable to clinically available drugs when in silico predictions were performed. The 50% cytotoxic dose of the compounds in human cells was between 1 and 20 μM (clinically relevant concentrations for gold compounds). Three gold(I) compounds inhibited viral infectivity at non-toxic concentrations and two gold(III) compounds did so at cytostatic (anti-proliferative mechanism that is also antiviral) concentrations. In the immunomodulatory assay, cytokine levels were altered by five compounds with one gold(I) and a gold(III) compound significantly reducing the frequency of CD4+ cells (an anti-viral function) from HIV+ donors (p= 0.005 and 0.027 respectively) when multi-parametric flow cytometry was performed. Inhibition of RT activity was predicted in in silico studies to be through interactions with the ribonuclease (RNase) H site although with poor stereochemical orientation while favourable binding predictions with the IN cofactor binding site were observed for some gold(III) complexes. Compounds predicted to interact with the RNase H site of RT and the IN cofactor site require structural modification to improve drug-likeness and binding affinity. The drug-like compound(s) which inhibited viral infectivity and lowered CD4+ cell frequency have potential for incorporation into virostatic cocktails (combination of cytostatic and directly anti-viral agent). Cytostatic agents are known to be less prone to drug resistance and because they lower CD4+ cell frequency, such compounds can potentially limit HIV immune activation.
Thesis (PhD)--University of Pretoria, 2011.
Biochemistry
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15

Zinser, Caroline Magdalene. "Palladium and gold N-heterocyclic carbene complexes : synthesis and catalytic applications." Thesis, University of St Andrews, 2019. http://hdl.handle.net/10023/17066.

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Zou, Taotao, and 邹滔滔. "Anti-cancer N-heterocyclic carbene complexes of gold(III), gold(I) and platinum(II) : thiol "switch-on" fluorescent probes, thioredoxin reductase inhibitors and endoplasmic reticulum targeting agents." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2015. http://hdl.handle.net/10722/208614.

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17

Li, Ka-lei Carrie. "In vitro and in vivo studies of cytotoxic and anti-angiogenic cyclometalated gold(III) and gold(III) porphyrin complexes." Click to view the E-thesis via HKUTO, 2008. http://sunzi.lib.hku.hk/hkuto/record/B39634577.

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18

Li, Ka-lei Carrie, and 李嘉莉. "In vitro and in vivo studies of cytotoxic and anti-angiogenic cyclometalated gold(III) and gold(III) porphyrin complexes." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2008. http://hub.hku.hk/bib/B39634577.

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19

Chan, Chi-keung. "Structure, photophysical and theoretical studies of polynuclear CU(I), AG(I) and AU(I) metal complexes /." Hong Kong : University of Hong Kong, 1997. http://sunzi.lib.hku.hk/hkuto/record.jsp?B18037422.

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20

Li, Chi-kwan. "Gold(I) and Gold(II) phosphine complexes exhibiting weak AuI ... AuI interactions and unsupported AuII-AuII bonds : syntheses, spectroscopy, host-guest chemistry and reactivity studies /." Hong Kong : University of Hong Kong, 2002. http://sunzi.lib.hku.hk/hkuto/record.jsp?B25155295.

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21

Dupuy, Stéphanie. "N-heterocyclic carbene gold hydroxide complexes as bond activation reagents." Thesis, University of St Andrews, 2014. http://hdl.handle.net/10023/6613.

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Although known since the 1930s, organogold chemistry has been dormant until recently, primarily due to preconceptions about the inertness of gold in transformations. However, this last decade has witnessed the emergence of a Golden Age with the development of a wealth of reports on gold in a plethora of reactions. In recent years, the drive for more atom- and step-economical and environmentally friendly reactions has become a field of intense research. In our on-going research on well-defined transition metal complexes bearing NHC ligands, our group recently discovered a new gold(I) hydroxide complex [Au(OH)(IPr)] (1a) that can be easily synthesised from the chloride precursor [AuCl(IPr)] (1b). A preliminary survey of the reactivity of this gold synthon has demonstrated interesting reactivity that holds great potential in bond activation reactions and the development of useful synthetic methods. Simplistically, this gold hydroxide complex can be seen as a strong Brønsted base. This thesis is dedicated to an in-depth examination of the reactivity of this complex in base-free bond activation reactions. Two themes predominate in the following chapters: the first part demonstrates the activity of gold(I) hydroxide as a bond activation agent to readily and efficiently access organogold complexes while the second part studies the reactivity of this compound in decarboxylation processes with carboxylic acids. Chapter 2 and 3 were dedicated to the development of new synthetic routes to access organogold complexes via base-free transmetalation reactions with organoborons and silanes using 1a. The combination of experimental and computational studies allowed identification and isolation of key intermediates in these reactions. Chapter 4 can be seen as a transition between the development of novel methodologies to synthesise aryl and heteroarylgold complexes and the first steps of gold hydroxide 1a as mediator in decarboxylation reaction. As a result, a novel mode of reactivity for gold was discovered and the synthetic route developed constitutes one of the greenest procedures to prepare organogold complexes with the generation of water and CO₂ as only side products. Chapter 5 and 6 venture further into the exploration of 1a in decarboxylation reactions and detail the development of a catalytic process for the protodecarboxylation reaction and subsequent mechanistic investigations of this reaction through stoichiometric experiments and kinetic and computational studies.
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22

Higginbotham, Mary Lynn. "Preclinical pharmacokinetic and tolerance assessment and phase I clinical trial of MU-gold, a novel chemotherapeutic agent /." Free to MU Campus, others may purchase, 2004. http://wwwlib.umi.com/cr/mo/fullcit?p1421141.

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23

Chan, Chui-ling. "Synthesis and luminescence studies of homo- and heteronuclear complexes of gold and copper /." Hong Kong : University of Hong Kong, 1998. http://sunzi.lib.hku.hk/hkuto/record.jsp?B20567698.

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24

Yip, Sung-kong. "Design, synthesis, characterization and luminescence properties of alkynylgold(I) complexes strategies towards supramolecular architectures and host guest chemistry /." Click to view the E-thesis via HKUTO, 2005. http://sunzi.lib.hku.hk/hkuto/record/B31941734.

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Lee, Wai-kit. "Syntheses, photophysics and photochemistry of polynuclear d10 complexes of copper(I) and gold(I) /." Hong Kong : University of Hong Kong, 1995. http://sunzi.lib.hku.hk/hkuto/record.jsp?B17665589.

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26

Sayahtaheri, Sousan. "Gold Compounds and Rheumatoid Arthritis Murine Studies of the Immune Response to Gold Sodium Thiomalate." Thesis, North Texas State University, 1986. https://digital.library.unt.edu/ark:/67531/metadc500824/.

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Balb/c normal mice were used to study the effects of gold sodium thiomalate (GST) on intact, nonadherent, and adherent mononuclear spleen cells. The three populations were tested for the following aspects: in vitro effects of GST on the mitogen-triggered DNA synthesis; intracellular levels of cyclic AMP; and chemotaxis ability. These studies showed that GST inhibited the proliferative responses of all three populations as the concentration of GST increased. Cyclic AMP levels in the nonadherent population increased as the GST concentration increased. GST had a biphasic effect on the adherent population. At concentrations of 5 and 10 jag/ml, GST suppressed the cyclic AMP levels, and at concentration of 50 pg/ml it enhanced the cyclic AMP levels. GST had no effect on the cyclic AMP levels in the intact mononuclear spleen cells. GST appeared to have an inhibitory effect on the chemotaxis ability of all three populations of spleen cells.
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27

Kui, Chi-fai. "Non-covalent weak interactions in group IV, PT(II) and AU(I) organometallic complexes synthesis, structures and properties /." Click to view the E-thesis via HKUTO, 2005. http://sunzi.lib.hku.hk/hkuto/record/B32021331.

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28

Liu, Li. "The chemistry of luminescent mercury (II) alkynyl complexes and their platinum (II) and gold (I) counterparts." HKBU Institutional Repository, 2005. http://repository.hkbu.edu.hk/etd_ra/627.

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29

Hung, Ling-ling. "Novel luminescent cyclometalated gold (III) alkynyls design, synthesis, photophysics and their multinuclear assemblies /." Click to view the E-thesis via HKUTO, 2007. http://sunzi.lib.hku.hk/hkuto/record/B3963453X.

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30

Shum, Yuen-ting. "Functionalized platinum (II) and gold (I) acetylide complexes structural and spectroscopic properties and anticancer activities /." Click to view the E-thesis via HKUTO, 2007. http://sunzi.lib.hku.hk/hkuto/record/B38639865.

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Shum, Yuen-ting, and 岑婉婷. "Functionalized platinum (II) and gold (I) acetylide complexes: structural and spectroscopic properties andanticancer activities." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2007. http://hub.hku.hk/bib/B38639865.

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Hung, Ling-ling, and 熊靈玲. "Novel luminescent cyclometalated gold (III) alkynyls: design, synthesis, photophysics and their multinuclearassemblies." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2007. http://hub.hku.hk/bib/B3963453X.

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33

He, Xiaoming. "Design, synthesis and characterization of alkynyl- and thiolato- gold (I) complexes with various receptor groups for host-guest chemistry." Click to view the E-thesis via HKUTO, 2010. http://sunzi.lib.hku.hk/hkuto/record/B43571979.

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Cheung, Kai-leung. "Syntheses and luminescence studies of di- and polynuclear gold(1) and copper(1) complexes, design strategies towards metalloreceptors and mixed-metal complexes /." Hong Kong : University of Hong Kong, 2001. http://sunzi.lib.hku.hk/hkuto/record.jsp?B23736136.

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35

Naoe, Saori. "Synthesis of Fused-Ring Compounds through Gold-Catalyzed Cascade Reactions." 京都大学 (Kyoto University), 2016. http://hdl.handle.net/2433/215495.

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36

Price, Gregory Arthur. "Routes to organogold compounds and gold catalysed A3-coupling reactions." Thesis, University of Manchester, 2013. https://www.research.manchester.ac.uk/portal/en/theses/routes-to-organogold-compounds-and-gold-catalysed-a3coupling-reactions(4b552b2f-0053-4449-9421-71116441850c).html.

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A new route to the synthesis of cyclometallated gold(III) complexes containing functionalised (2-dimethylaminomethyl)phenyl ligands is described. The synthesis of 2-Me2NCH2-C6H4AuCl2 (8a), 2-Me2NCH2-5-CH3-C6H3AuCl2 (49), 2-Me2NCH2-5-CF3-C6H3AuCl2 (50) and 2-Me2NCH2-5-OMe-C6H3AuCl2 (51) has been accomplished via transmetallation from the corresponding boroxines to sodium tetrachloroaurate in aqueous acetonitrile. This protocol gives comparable yields to those obtained via transmetallation from an organomercurial. However this route is advantageous as it avoids the use of extremely toxic mercury compounds. The novel bimetallic tin(IV) complexes 1,4-(SnPh3)2-2,5-(NMe2CH2)2-C6H2 (66),1,4-(SnMe3)2-2,5-(NMe2CH2)2-C6H2 (67) and 1,4-(SnMe2Cl)2-2,5-(NMe2CH2)2-C6H2 (68) have been synthesised by in-situ quenching of 1,4-(Li)2-2,5-(NMe2CH2)2-C6H2 (57) with two equivalents of ClSnPh3, ClSnMe3 or Cl2SnMe2 respectively. Transmetallation from 1,4-(SnMe2Cl)2-2,5-(NMe2CH2)2-C6H2 (68) with two equivalents of sodium tetrachloroaurate in refluxing acetonitrile resulted in the formation of the relatively insoluble di-gold(III) complex 1,4-(AuCl2)2-2,5-(NMe2CH2)2-C6H2 (71). The novel bisphosphine 1,4-(PPh2)2-2,5-(NMe2CH2)2-C6H2 (69) has also been prepared by in-situ quenching of 1,4-(Li)2-2,5-(NMe2CH2)2-C6H2 (57) with two equivalents of ClPPh2. 69 was reacted with ClAu(THT) to form the novel di-gold(I) phosphine complex 1,4-(ClAuPPh2)2-2,5-(NMe2CH2)2-C6H2 (70) in excellent yield. The catalytic activity of a variety of gold(I) and gold(III) complexes in the A3-coupling of aldehydes, amines and alkynes has been investigated. 2-Me2NCH2-C6H4AuCl2 (8a) was found to be an effective catalyst for A3-couplings, with H2O as solvent, giving essentially quantitative conversions after 24 h. The couplings were tolerant to a diverse range of substrates. A range of chiral Au(III) and Au(I) complexes were prepared and screened in the reaction of benzaldehyde, dibenzylamine and phenylacetylene. In all cases no discernible ee was observed. A series of A3-coupling reactions catalysed by 8a, Na[AuCl4] .2H2O and [AuCCPh]n (139) were also monitored by 1H NMR spectroscopy and this data suggests a common, catalytically active species, is formed during these reactions. The addition of PPh3 to the gold catalysed couplings was found to severely retard the reactions. In contrast the use of chloroform as the solvent resulted in significant improvements to the rate of reaction. Overall the data collected provides a mechanistic insight into the development of asymmetric A3-coupling reactions. The evidence suggests that a single universal catalytically active acetylide species is formed from both Au(I) and Au(III) precursors.
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Cheng, Chung-chin. "Syntheses and photophysics of luminescent polynuclear coinage metal complexes with chalcogen and pnictogen containing bridging ligands /." Hong Kong : University of Hong Kong, 2001. http://sunzi.lib.hku.hk/hkuto/record.jsp?B22956372.

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38

Chan, On-yee, and 陳安怡. "Bioconjugation reactions of peptides and proteins mediated by manganese, ruthenium and gold compounds." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2010. http://hub.hku.hk/bib/B46539773.

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39

Wang, Mingzhong, and 汪明中. "Selective alkylation of indoles catalyzed by gold (I) phosphine complexes and ruthenium (II) porphyrin complexes." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2010. http://hub.hku.hk/bib/B45699501.

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40

Li, Chi-kwan, and 李志君. "Gold(I) and Gold(II) phosphine complexes exhibiting weak AuI... AuI interactions and unsupported AuII-AuII bonds: syntheses, spectroscopy, host-guest chemistry and reactivity studies." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2002. http://hub.hku.hk/bib/B31243332.

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41

李維傑 and Wai-kit Lee. "Syntheses, photophysics and photochemistry of polynuclear d10 complexes of copper(I) and gold(I)." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1995. http://hub.hku.hk/bib/B31234264.

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42

Veenboer, Richard M. P. "Synthesis, study and application of NHC-gold(I) complexes." Thesis, University of St Andrews, 2017. http://hdl.handle.net/10023/12169.

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The development of procedures for the synthesis of valuable organic molecules constitutes an important part of chemistry. The goal of improving the efficiency of existing methodologies can be fulfilled by use of metal catalysts. Recent developments in the field of homogeneous gold catalysis have contributed to these efforts and continued investigations assure future innovations. Chapter 1 summarises the properties of gold and ligand-supported gold(I) complexes and demonstrates how a detailed understanding of its reactivity and possible bonding interactions with various substrates facilitates the development of well-defined catalytic systems. Particular attention is given to N-heterocyclic carbenes, highly tunable ligands that stabilise a wide range of different transition metal complexes. Three chapters describe syntheses and studies of known and new complexes. Chapter 2 discusses expedient syntheses of key NHC-gold(I) complexes and catalysts. Chapter 3 constitutes studies to the behaviour of the commonly used tetrafluoroborate counterion in a particular IPrCl -gold(I) complex. Chapter 4 de- scribes the synthesis of a range of IPr-gold(I) carbanion complexes from the widely studied IPr-gold(I) hydroxide synthon, the study of their properties and exploration of their reactivity. Catalytic applications in transformations of alkynes and alcohols are described in the last three chapters. Chapter 5 details the development of efficient NHC-gold(I)-catalysed procedures for the synthesis of vinyl ethers through addition reactions of aliphatic and benzylic alcohols to alkynes. Benzylic alcohols were found to undergo gold-catalysed dehydration under specific conditions and Chapter 6 discloses the NHC-gold(I)-catalysed dehydrative formation of ethers from phenols and benzylic alcohols. Appendix A describes preliminary explorations to the complimentary use of Brønsted acidic compounds as catalysts for the formation of products with new C – C bonds from benzylic alcohols and phenols.
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Lum, Ching-tung. "Treatment of hepatocellular carcinoma with a novel gold compound." Click to view the E-thesis via HKUTO, 2005. http://sunzi.lib.hku.hk/hkuto/record/B30699927.

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Yan, Jing, and 严静. "The anticancer properties of gold (III) complexes with tridentate cyclometalated, porphyrinato and glycosylated ligands." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2011. http://hub.hku.hk/bib/B4587265X.

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Tian, Songhai, and 田松海. "Proteomic and pharmacological analyses of the mechanism of actions of anticancer gold(I) complexes." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2014. http://hdl.handle.net/10722/206471.

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Gold complexes have a long history of being used as therapeutic agents, especially in applications against immune diseases such as rheumatoid arthritis. In 1979, an oral gold(I) drug – auranofin (AuRF, brand name as Ridaura®) – was demonstrated to exhibit anticancer properties. Since then, a considerable number of gold(I) complexes have been reported to show remarkable anticancer activities, but the understanding of their mechanism of actions is limited. In the present study, AuRF and several other anticancer gold(I)-phosphine complexes including AuPEt ([Au(triethylphosphine)Cl]) were demonstrated to induce autophagy – a cellular catabolic process of macromolecules and organelles through lysosomal degradation. The induced autophagy involved the accumulation of autophagosomes, which was mediated by the enhancement of autophagy initiation rather than by the blockage of autophagosomes maturation. Moreover, the AuRF and AuPEt induced autophagy was demonstrated to have a pro-survival effect for the cancer cells. To better explore the mechanism of actions of AuRF and other anticancer gold(I) complexes, a subcellular fractionation-based proteomic approach has been developed and optimized. This approach combined the use of subcellular fractionation, protein extraction, HPLC-LTQ-Orbitrap mass spectrometry, and bottom-up protein identification and quantification. By using this approach, the proteome coverage was increased, the complexities of the sub-proteomes were reduced, and the low-abundant organelle proteins were enriched. The nuclear sub-proteomes of AuRF-treated or AuPEt-treated cells were analyzed to identify the significantly regulated transcription regulators and the signaling pathways involved. The analysis delineates the possible AuRF-activated anticancer pathways involving up-regulation of the tumor suppressor cyclin-dependent kinase inhibitor 2A (〖p14〗^ARF), inhibition of the E2F transcription activity, blocking of the translocation of E3 ubiquitin-protein ligase (MDM2) from nucleus to cytoplasm and induction of the tumor suppressor p53. Furthermore, the KeyNode-based pathway analysis was applied to analyze the whole proteomes obtained from merging the sub-proteomes. Alongside the p53 pathway and E2F network, the regulation of 3-hydroxy-3-methylglutaryl-CoA reductase (HMGCR, the rate-limiting enzyme of cholesterol biosynthesis) is one of the most up-regulated pathways of AuRF treatment. AuRF also showed significant inhibition to HMGCR activity in vitro with an IC50 value at the micromolar level. The effects of AuRF and AuPEt on the high mobility group box-1 protein (HMGB1), which exhibits distinct functions dependent on its cellular locations, were investigated. Treatment of cells with AuRF or AuPEt resulted in down-regulation of nuclear HMGB1, which is associated with p53-dependent cytotoxicities. The cytoplasmic HMGB1, which can induce autophagy, was found to be up-regulated. The levels of secreted HMGB1, which exhibits pro-inflammatory properties, were reduced, possibly contributing to anti-rheumatoid arthritis actions of AuRF. Collectively, the pharmacological and proteomic analyses in this research of AuRF and other anticancer gold(I) complexes supplement the current knowledge of their mechanism of actions.
published_or_final_version
Chemistry
Doctoral
Doctor of Philosophy
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46

Chan, Sau-han. "Non-heme iron(III) and gold(III) complexes with dicarboxamide ligands synthesis, structures and anti-cancer properties /." Click to view the E-thesis via HKUTO, 2007. http://sunzi.lib.hku.hk/HKUTO/record/B39557984.

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47

Yip, Sung-kong, and 葉崇江. "Design, synthesis, characterization and luminescence properties of alkynylgold(I) complexes: strategies towardssupramolecular architectures and host guest chemistry." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2005. http://hub.hku.hk/bib/B31941734.

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48

Chan, Sau-han, and 陳秀嫻. "Non-heme iron(III) and gold(III) complexes with dicarboxamide ligands: synthesis, structures and anti-cancerproperties." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2007. http://hub.hku.hk/bib/B39557984.

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49

Chan, Chi-keung, and 陳志強. "Structure, photophysical and theoretical studies of polynuclear CU(I),AG(I) and AU(I) metal complexes." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1997. http://hub.hku.hk/bib/B31235554.

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Stoica, Otilia Violeta. "Synthesis of Large Hydroacenes and Related Compounds Using Gold(I) Catalysis." Doctoral thesis, Universitat Rovira i Virgili, 2021. http://hdl.handle.net/10803/671555.

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Aquesta tesis doctoral presenta el desenvolupament de noves estratègies per a la síntesis d’hidrocarburs aromàtics policíclics així com acens i anàlegs. En primer lloc, una nova síntesis iterativa ha sigut desenvolupada per a preparar acens llargs no substituïts. Aquesta, és basada en la cicloaddició [4+2] de 1,7-enins catalitzada per Au(I) estudiada prèviament al nostre grup i va permetre la formació de nous hidroacens, desde tridecacé-H8 fins heptadecacé-H10. La deshidrogenació en una superfície d’Au(111) del primer precursor va generar el compost tridecacé, l’acé més llarg conegut fins ara. Els precursors d’altres derivats d’acens que pertanyen a altres categories, com indecacens, acens que contenen ciclobutadiens o heteroacens han sigut obtinguts utilitzant la cicloaddició [4+2] de nous 1,7-enins. La formació i caracterització dels acens en superfícies metàl·liques ha sigut investigada mitjançant tècniques de microscòpia electrònica. Dos anàlegs de la primera classe, s-indacé[1,2-b:5,6-b’]ditetracé i as-indaceno[2,3-b:6,7-b’]ditetracé, han sigut obtinguts per cicloaddició d’un precursor bis-dihidrotetracé en una superfície d’Au(111). S’ha observat que l’últim derivat d’indacé participa en cicloaddicions intermoleculars sense precedents en superfícies, produint molècules en forma de T. La reacció també te lloc quan pentacé i octacé s’utilitzen com dienòfils. Finalment, la orto-alquilació C–H d’aldehids aromàtics catalitzada per Rh(III) ha sigut investigada per a obtenir nous substrats per a la síntesis de poliarens. La reacció està promoguda per un grup director transitori que ha fet possible construir una varietat de compostos mono- i doblement alquinilats. Els inals obtinguts han sigut utilitzats en la preparació de dibenzopentalens substituïts, isoquinolines, indols i indolines.
Esta tesis doctoral presenta el desarrollo de nuevas estrategias para la síntesis de hidrocarburos aromáticos policíclicos, incluyendo acenos y sus análogos. En primer lugar, una nueva síntesis iterativa ha sido llevada a cabo para preparar acenos largos no sustituidos, en base a la cicloadición formal [4+2] de 1,7-eninos catalizada por Au(I) estudiada previamente por nuestro grupo. Esto permitió la obtención de nuevos hidroacenos, desde tridecaceno-H8 hasta heptadecaceno-H10. La deshidrogenación en una superficie de Au(111) del primer precursor produjo el compuesto tridecaceno, el aceno más largo conocido hasta ahora. Los precursores de otros derivados de acenos perteneciendo a otras categorías, como indacenos, acenos que contienen ciclobutadienos o heteroacenos han sido obtenidos usando nuestra cicloadición formal [4+2] de nuevos 1,7-eninos. La generación y caracterización de los acenos en superficies metálicas ha sido investigada utilizando técnicas de microscopia electrónica. Dos análogos de la primera clase, s-indaceno[1,2-b:5,6-b’]ditetraceno y as-indaceno[2,3-b:6,7-b’]ditetraceno, han sido obtenidos por cicloadición de un precursor bis-dihidrotetraceno en una superficie de Au(111). Se ha observado que el último derivado de indaceno participa en cicloadiciones intermoleculares sin precedentes en superficies, produciendo moléculas en forma de T. La reacción también tiene lugar cuando pentaceno y octaceno se usan como dienófilos. Finalmente, la orto-alquinilación C–H de aldehídos aromáticos catalizada por Rh(III) ha sido investigada para obtener nuevos sustratos para la síntesis de poliarenos. La reacción está promovida por un grupo director transitorio y permitió construir una variedad de compuestos mono- y doblemente alquinilados. Los inales obtenidos han sido usados en la preparación de dibenzopentalenos sustituidos, isoquinolinas, indoles e indolinas.
This Doctoral Thesis covers the design of novel strategies for the synthesis of polycyclic aromatic hydrocarbons, such as acenes and their analogues. For instance, a new iterative synthesis was elaborated for the preparation of higher unsubstituted hydroacenes, based on our previously developed gold(I)-catalyzed formal [4+2] cycloaddition of aryl-tethered 1,7-tetraenynes, and enabled the formation of unprecedented hydroacenes, from tridecacene-H8 to heptadecacene-H10. The Au(111) surface-assisted dehydrogenation of the former precursor afforded the parent tridecacene, the longest acene known until now. The precursors of acene derivatives belonging to diverse categories, such as indacenes, cyclobutadiene-containing acenes or heteroacenes have been acquired by applying our gold(I)-catalyzed formal [4+2] cycloaddition to newly developed 1,7-enynes. The surface-assisted formation of the parent acenes has already been investigated or is currently ongoing. Two analogues from the first category, s-indaceno[1,2-b:5,6-b’]ditetracene and as-indaceno[2,3-b:6,7-b’]ditetracene, were obtained through cycloaddition of a bis-dihydrotetracene precursor on a Au(111) surface. The latter indacene derivative was found to undergo an outstanding intermolecular cycloaddition, rendering T-shaped molecules. The reaction was also successful when pentacene and octacene were employed as dienophiles. Finally, the Rh(III)-catalyzed ortho C–H alkynylation of aromatic aldehydes was investigated in order to obtain new versatile building blocks for the synthesis of polyarenes. Enabled by the formation of an imine as transient directing group, this transformation provided a wide variety range of mono- and di-alkynylated products. The acquired ynals were then successfully engaged in the preparation of substituted dibenzopentalenes, isoquinolines, indoles and indolines.
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