UvA-DARE (Digital Academic Repository) Fluorogenic organocatalytic reactions Raeisolsadati Oskouei, M. Link to publication

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1 UvA-DARE (Digital Academic Repository) Fluorogenic organocatalytic reactions Raeisolsadati Oskouei, M. Link to publication Citation for published version (APA): Raeisolsadati Oskouei, M. (2017). Fluorogenic organocatalytic reactions. General rights It is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulations If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. UvA-DARE is a service provided by the library of the University of Amsterdam ( Download date: 08 Apr 2019

2 Invitation To the public defence of my thesis entitiled: Fluorogenic Organocatalytic Reactions Fluorogenic Organocatalytic Reactions Fluorogenic Organocatalytic Reactions On Tuesday 25th of April at 10:00 a.m. Agnietenkapel, Oudezijds Voorburgwal 231, 1012 EZ Amsterdam Mina Raeisolsadati Oskouei Mina Raeisolsadati Oskouei Paranymphs: Mina Raeisolsadati Oskouei Dongdong Zheng Jing Zuo Fluorogenic Organocatalytic Reactions Processed on: L-bw-Oskouei

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4 Fluorogenic Organocatalytic Reactions Mina Raeisolsadati Oskouei Fluorogenic Organocatalytic Reactions Fluorogenic Organocatalytic Reactions Mina Raeisolsadati Oskouei L-bw-Oskouei Processed on: Invitation Jing Zuo Dongdong Zheng Paranymphs: Mina Raeisolsadati Oskouei Agnietenkapel, Oudezijds Voorburgwal 231, 1012 EZ Amsterdam On Tuesday 25th of April at 10:00 a.m. Fluorogenic Organocatalytic Reactions To the public defence of my thesis entitiled:

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6 Fluorogenic Organocatalytic Reactions ACADEMISCH PROEFSCHRIFT ter verkrijging van de graad van doctor aan de Universiteit van Amsterdam op gezag van de Rector Magnificus prof. dr. ir. K.I.J. Maex ten overstaan van een door het College voor Promoties ingestelde commissie, in het openbaar te verdedigen in de Agnietenkapel op dinsdag 25 april 2017 te 10:00 uur door Mina Raeisolsadati Oskouei geboren te Tabriz, Iran

7 Promotiecommissie: Promotor: Prof. dr. A. M. Brouwer Universiteit van Amsterdam Copromotor: Prof. dr. H. Hiemstra Universiteit van Amsterdam Overige leden: Prof. dr. W. J. Buma Universiteit van Amsterdam Dr. M. A. Fernández-Ibáñez Universiteit van Amsterdam Prof. dr. J. H. van Maarseveen Universiteit van Amsterdam Prof. dr. F. P. J. T. Rutjes Radboud Universiteit Prof. dr. S. Woutersen Universiteit van Amsterdam Faculteit der Natuurwetenschappen, Wiskunde en Informatica The research covered in this thesis was conducted in the Molecular Photonics group at the Van t Hoff Institute for Molecular Sciences, University of Amsterdam.

8 To Karim and Juliette

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10 Contents Abbreviations Chapter 1. Introduction Organocatalysis Cinchona alkaloid based organocatalysts Thiourea based organocatalysts Fluorescence spectroscopy Fluorogenic reactions BODIPYs as the suitable candidates for fluorogenic reactions Outline of the research 13 References.. 15 Chapter 2. Experimental methods and characterization General information Synthesis of the substrate BODIPYs Synthesis of compound Synthesis of compound Synthesis of compound Synthesis of compound Synthesis of compound Synthesis of compound Synthesis of compound Synthesis of compound Synthesis of the catalysts Synthesis of dimethyl amino cyclohexyl amine Synthesis of catalyst Synthesis of catalyst Synthesis of catalysts Synthesis of catalyst Synthesis of catalyst General procedure for Immobilization of the catalysts on the surface of glass cover slips Cover slips cleaning Cover slips modification Catalysts immobilization Synthesis of catalyst Synthesis of the product BODIPYs General procedure for the synthesis of compound General procedure for the synthesis of compound General procedure for the synthesis of compound General procedure for the synthesis of compound General procedure for the synthesis of compound i

11 General procedure for the synthesis of compound General procedure for the synthesis of compound References 40 Chapter 3. Fluorescence turn-on in organocatalytic Michael reactions Introduction Michael reaction of compound 15 with benzyl mercaptan in the presence of different organocatalysts Following the Michael reaction of compound 15 with benzyl mercaptan in the presence of hydrogen bond donating organocatalysts using fluorescence spectroscopy Following the Michael reaction of compound 15 with benzyl mercaptan in the presence of immobilized organocatalysts using fluorescence spectroscopy Following the Michael reaction of compound 15 with benzyl mercaptan in the presence of a fluorescent organocatalyst Michael addition reaction between compound 17 and benzyl mercaptan Michael addition of reaction compound 15 and dimethylmalonate Reaction of the BODIPY-Maleimide and BODIPY-Nitroalkene with carbon nucleophiles Conclusion.. 66 References. 66 Chapter 4. Organocatalytic synthesis of fluorescent chromenes Chromenes and fluorogenic reactions Fluorescent Chromenes References Chapter 5. Organocatalytic Biginelli reaction Introduction Fluorescent derivative of DHPM Discussion Conclusion.. 98 References. 98 Chapter 6. Towards Single Molecule Detection of Organocatalytic Reactions Introduction Imaging with TIRFM Experiment Design TIRFM of organocatalytic Michael addition of benzyl mercaptan to compound Conclusion References. 119 ii

12 Publication from this Thesis Summary Samenvatting Acknowledgments 133 iii

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14 Abbreviations AIBN BINOL BnCl Boc-L-Proline BODIPY BzCl CFM DCE DCM DDQ DHPMs DIEA DMF DMSO EDCI ee emccd EtOAc FRET HOAc HOBt HPLC mcpba NOBIN NSOM PET PMT scmos SEM TADDOLS TCSPC TFA TFAA THF TIRFM TLC Azobisisobutyronitrile 1,1 -Bi-2-naphthol Benzyl chloride N-(tert-Butoxycarbonyl)-L-proline Boron-dipyrromethene Benzoyl chloride Confocal microscopy Dichloroethane Dichloromethane 2,3-Dichloro-5,6-dicyanobenzoquinone Dihydropyrimidinones N,N-Diisopropylethylamine Dimethylformamide Dimethyl sulfoxide 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Enantiomeric excess Electron multiplying charge coupled device Ethyl acetate Förster resonance energy transfer Acetic acid Hydroxybenzotriazole High performance liquid chromatography 3-Chloroperbenzoic acid 2-Amino-2'-hydroxy-1,1'-binaphthyl Near-field scanning optical microscopy Photoinduced electron transfer Photomultiplier Scientific complementary metal oxide semiconductor Scanning electron microscopy α,α,α,α-tetraaryl-1,3-dioxolane-4,5- dimethanols Time-correlated single photon counting Trifluoroacetic acid Trifluoroacetic anhydride Tetrahydrofuran Total internal reflection fluorescence microscope Thin layer chromatography