DOCSLIB.ORG

Palladium-Catalyzed Asymmetric Allylic Amination. Development and Synthetic Applications

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Palladium-Catalyzed Asymmetric Allylic Amination. Development and Synthetic Applications PALLADIUM-CATALYZED ASYMMETRIC ALLYLIC AMINATION. DEVELOPMENT AND SYNTHETIC APPLICATIONS Sebastien Soriano Istat ADVERTIMENT. L'accés als continguts d'aquesta tesi doctoral i la seva utilització ha de respectar els drets de la persona autora. Pot ser utilitzada per a consulta o estudi personal, així com en activitats o materials d'investigació i docència en els termes establerts a l'art. 32 del Text Refós de la Llei de Propietat Intel·lectual (RDL 1/1996). Per altres utilitzacions es requereix l'autorització prèvia i expressa de la persona autora. En qualsevol cas, en la utilització dels seus continguts caldrà indicar de forma clara el nom i cognoms de la persona autora i el títol de la tesi doctoral. No s'autoritza la seva reproducció o altres formes d'explotació efectuades amb finalitats de lucre ni la seva comunicació pública des d'un lloc aliè al servei TDX. Tampoc s'autoritza la presentació del seu contingut en una finestra o marc aliè a TDX (framing). Aquesta reserva de drets afecta tant als continguts de la tesi com als seus resums i índexs. ADVERTENCIA. El acceso a los contenidos de esta tesis doctoral y su utilización debe respetar los derechos de la persona autora. Puede ser utilizada para consulta o estudio personal, así como en actividades o materiales de investigación y docencia en los términos establecidos en el art. 32 del Texto Refundido de la Ley de Propiedad Intelectual (RDL 1/1996). Para otros usos se requiere la autorización previa y expresa de la persona autora. En cualquier caso, en la utilización de sus contenidos se deberá indicar de forma clara el nombre y apellidos de la persona autora y el título de la tesis doctoral. No se autoriza su reproducción u otras formas de explotación efectuadas con fines lucrativos ni su comunicación pública desde un sitio ajeno al servicio TDR. Tampoco se autoriza la presentación de su contenido en una ventana o marco ajeno a TDR (framing). Esta reserva de derechos afecta tanto al contenido de la tesis como a sus resúmenes e índices. WARNING. Access to the contents of this doctoral thesis and its use must respect the rights of the author. It can be used for reference or private study, as well as research and learning activities or materials in the terms established by the 32nd article of the Spanish Consolidated Copyright Act (RDL 1/1996). Express and previous authorization of the author is required for any other uses. In any case, when using its content, full name of the author and title of the thesis must be clearly indicated. Reproduction or other forms of for profit use or public communication from outside TDX service is not allowed. Presentation of its content in a window or frame external to TDX (framing) is not authorized either. These rights affect both the content of the thesis and its abstracts and indexes. UNIVERSITAT ROVIRA I VIRGILI PALLADIUM-CATALYZED ASYMMETRIC ALLYLIC AMINATION. DEVELOPMENT AND SYNTHETIC APPLICATIONS Sebastien Soriano Istat SEBASTIEN SORIANO ISTAT PALLADIUM-CATALYZED ASYMMETRIC ALLYLIC AMINATION. DEVELOPMENT AND SYNTHETIC APPLICATIONS DOCTORAL THESIS Supervised by Dr. Sergio Castillón Miranda and Dra. Yolanda Díaz Giménez Departament de Química Analítica i Química Orgànica Tarragona, 2015 UNIVERSITAT ROVIRA I VIRGILI PALLADIUM-CATALYZED ASYMMETRIC ALLYLIC AMINATION. DEVELOPMENT AND SYNTHETIC APPLICATIONS Sebastien Soriano Istat UNIVERSITAT ROVIRA I VIRGILI PALLADIUM-CATALYZED ASYMMETRIC ALLYLIC AMINATION. DEVELOPMENT AND SYNTHETIC APPLICATIONS Sebastien Soriano Istat Departament de Química Analítica i Química Orgànica Facultat de Química c/ Marcel·lí Domingo, s/n 43007, Tarragona Els sotasignants Sergio Castillón Miranda, Catedràtic de Química Orgànica, i Yolanda Díaz Giménez, Professora Titular de Química Orgànica, del Departament de Química Analítica i Química Orgànica de la Universitat Rovira i Virgili, HAGO CONSTAR que el presente trabajo, titulado “Palladium-catalyzed asymmetric allylic amination. Development and synthetic applications”, que presenta Sébastien Soriano Istat. para la obtención del título de Doctor, ha sido realizado bajo mi dirección en el Departamento de Química Analítica y Orgánica de esta universidad. Tarragona, 6 de octubre de 2015 Dr. Sergio Castillón Miranda Dra. Yolanda Díaz Giménez UNIVERSITAT ROVIRA I VIRGILI PALLADIUM-CATALYZED ASYMMETRIC ALLYLIC AMINATION. DEVELOPMENT AND SYNTHETIC APPLICATIONS Sebastien Soriano Istat UNIVERSITAT ROVIRA I VIRGILI PALLADIUM-CATALYZED ASYMMETRIC ALLYLIC AMINATION. DEVELOPMENT AND SYNTHETIC APPLICATIONS Sebastien Soriano Istat El presente trabajo ha sido desarrollado con una beca BRDI de la Universidad Rovira i Virgili. Los siguientes proyectos han financiado el trabajo que se describe en esta tesis: New synthetic methods in carbohydrate chemistry. CTQ2008-01569-BQU Glycolipids and carbohydrates. New synthetic methods and biological applications. CTQ-2011-22872 Diseño de Catalizadores para una Química Sostenible: Una Aproximación Integrada (INTECAT). Consolider Ingenio (CSD2006-0003) UNIVERSITAT ROVIRA I VIRGILI PALLADIUM-CATALYZED ASYMMETRIC ALLYLIC AMINATION. DEVELOPMENT AND SYNTHETIC APPLICATIONS Sebastien Soriano Istat UNIVERSITAT ROVIRA I VIRGILI PALLADIUM-CATALYZED ASYMMETRIC ALLYLIC AMINATION. DEVELOPMENT AND SYNTHETIC APPLICATIONS Sebastien Soriano Istat ACKNOWLEDGEMENTS En primer lugar quiero agradecer mis directores, el Dr. Sergio Castillón y Dra. Yolanda Díaz por la oportunidad y confianza que me dieron de realizar mi tesis Doctoral en su grupo de investigación. Gracias por confiar en mi y brindarme su ayuda y consejos cuando los he necesitado. Su experiencia y formación me han aportado mucho durante estos años de desarrollo de mi tesis tanto a nivel profesional como personal. De igual forma quiero tener la oportunidad de agradecer al resto de profesores del grupo, Dra. Maribel Mateu y Dr. Omar Boutureira por sus buenos consejos y comentarios. Agradecer también a los profesores del grupo de Polímeros que han estado disponibles cuando los he necesitado durante estos años. Mi sincero agradecimiento también al personal administrativo y técnico del departamento: Juan Luis, Taïs, Olga, por facilitarme las aburridas gestiones durante mi estancia. Quería expresar un agradecimiento particular al dúo choc Avelina y Dúnia del departamento, por sus contribuciones mas humanas; gracias a vosotras dos por la alegría y el buen humor que siempre habéis llevado, los cotilleos, las risas, los cafés, las lentejas...habéis hecho que todo eso haya sido un poquito mas fácil. Gracias por lo que me habéis dado tanto a nivel profesional como personal..ha sido un placer coincidir con vosotras. No puedo olvidar al personal del Servicio de Recursos Científicos por su gran disponibilidad y colaboración. En particular a Ramón (RMN) y Irene (HPLC), quienes siempre se han mostrados muy amables y dedicado mucho de su tiempo. UNIVERSITAT ROVIRA I VIRGILI PALLADIUM-CATALYZED ASYMMETRIC ALLYLIC AMINATION. DEVELOPMENT AND SYNTHETIC APPLICATIONS Sebastien Soriano Istat No quiero olvidar a mis compañeros de laboratorio, a algunos de los que fueron compañeros en el inicio de esta experiencia: los cuatros I, Isabella, Isidro, Ismael e Irene y Míriam, el Dr. Pep, Mariam, Xavi y Joan, quienes con mucho humor han intentado enseñarme el idioma y las tradiciones catalanas. Sin olvidar los consejos, que debido a su experiencia, me han podido dar. Sin vosotros esto no hubiese sido lo mismo, se os ha echado mucho de menos! Gracias por compartir charlas, amistad y momentos de diversión! A mis compañeras extranjeras Xochlit y Araceli..gracias por tener siempre una sonrisa, ha sido un verdadero placer compartir esta experiencia con vosotras! No voy a olvidarte Hotty, muchas gracias por todo, siempre has estado ahí cuando lo he necesitado, gracias por las correcciones y esta amistad que compartimos ahora.. No quiero olvidar a mis compañeros de laboratorio actuales, especialmente a Jordi por sus consejos nutritivos, David por esas numerosas apuestas perdidas, Jordi C., Adrià, Macarena, Irene y Margarita...gracias por todo y os deseo mucha suerte en lo que os queda de viaje! Por último, pero no por eso menos importante, agradecer a mis compañeros de Polímeros por todos los momentos vividos. Gracias a Camilo, Mariluz, Rodolfo, Cristina, Adrià, Marc, Carmen, Lorena y a mis amigas turcas, Alev y Zeynep, por hacerme reír y escucharme cuando lo necesitaba, espero que guardaremos contacto!! Un agradecimiento especial a mi amigo George T. por estar siempre ahí cuando lo he necesitado, me has aportado tanto que no se como agradecerte...espero poder seguir contando contigo durante muchos años. Merci por haberme dedicado mucho de tu tiempo para esa tesis..sin ti no se como lo hubiera podido lograr! No olvidare de agradecer a mis dos amigos "Los Martinez", Dani y kiki por su apoyo incondicional y una amistad excepcional! Gracias por UNIVERSITAT ROVIRA I VIRGILI PALLADIUM-CATALYZED ASYMMETRIC ALLYLIC AMINATION. DEVELOPMENT AND SYNTHETIC APPLICATIONS Sebastien Soriano Istat deconcentrarme cada fin de semana...No ahora va en serio..merci a los dos! Il en va de soi que je n'oublierai pas mes plus fidèles poto belges pour m'avoir soutenu moralement durant cette periode. Si j'écris ces quelques mots c'est pour vous exprimer toute ma gratitude. Merci a toi HG pour ces nombreuses heures passées sur viber, a Vince pour avoir toujours été present ainsi que pour ses nombreux conseils. Une petite dedic aux Jallets aussi juste pour rire. Muchas gracias a mi Mamy chérie y Mireia por aguantarme durante tantos años. Por darme todo el apoyo
Load more

Recommended publications
  • Palladium-Catalyzed Tsuji-Trost Allylation of J-Borylated Allyl Acetates
    ANNÉE 2013 THÈSE / UNIVERSITÉ DE RENNES 1 sous le sceau de l’Université Européenne de Bretagne pour le grade de DOCTEUR DE L’UNIVERSITÉ DE RENNES 1 Mention : CHIMIE Ecole doctorale Sciences de la Matière de Rennes présentée par Krishna Kishore Kukkadapu UMR 6510 CNRS Chimie et Photonique Moléculaires UFR Sciences et Propriétés de la Matière Thèse soutenue à Rennes Gamma-borylated le Jeudi 6 juin 2013 allylic acetates as 3 devant le jury composé de : Véronique BELLOSTA carbon functionalized Professeur –ESPCI / rapporteur units : synthesis and Stéphane PELLET-ROSTAING Chargé de recherche CNRS à l’ICSM-CEA / applications rapporteur Florence MONGIN Professeur à l’Université de Renne1 / / examinateur Mathieu PUCHEAULT Chargé de recherche CNRS / examinateur Michel VAULTIER Directeur de recherche CNRS/ / directeur de thèse 1 Table of contents : Résumé de la thèse en français 5 Acknowledgements: 22 Abbreviations: 24 General Introduction: 27 PART ͲA 30 Chapter I: Bibliography 30 I. 1. Synthesis &applications of JͲborylated allylic electrophiles: 31 I. 1. i. Synthesis of JͲborylated allylic electrophiles: 31 I. 1. ii. Applications of JͲborylated allylic electrophiles: 33 I. 1. ii. a. In iridium catalysis: 33 I. 1. ii. b. In copper catalysis: 37 I. 1. ii. c. In palladium catalysis: 39 I. 1. ii. d. In Grignard reaction: 41 I. 1. ii. e. In Diels Alder reaction: 42 I. 1. ii. f. In Mitsunobu reaction: 43 I. 1. ii. g. In cyclopropane synthesis: 46 I. 2. Tsuji ͲTrost Allylation: 48 I. 2. i. Stereochemistry in Tsuji ͲTrost allylation: 51 I. 2. ii. Regioselectivity in Tsuji ͲTrost allylation: 52 I. 2. iii.
    [Show full text]
  • Stretchable Chiral Pockets for Palladium-Catalyzed Highly Chemo- and Enantioselective Allenylation ✉ ✉ Yuchen Zhang1, Xue Zhang2 & Shengming Ma 1,2
    ARTICLE https://doi.org/10.1038/s41467-021-22498-1 OPEN Stretchable chiral pockets for palladium-catalyzed highly chemo- and enantioselective allenylation ✉ ✉ Yuchen Zhang1, Xue Zhang2 & Shengming Ma 1,2 Pyrazolones are a vital class of heterocycles possessing various biological properties and much attention is paid to the diversified synthesis of enantiopure pyrazolone derivatives. We describe here the development of diphenylphosphinoalkanoic acid based chiral bisphosphine 1234567890():,; ligands, which are successfully applied to the palladium-catalyzed asymmetric allenylation of racemic pyrazol-5-ones. The reaction affords C-allenylation products, optically active pyrazol- 5-ones bearing an allene unit, in high chemo- and enantioselectivity, with DACH-ZYC-Phos- C1 as the best ligand. The synthetic potential of the C-allenylation products is demonstrated. Furthermore, the enantioselectivity observed with DACH-ZYC-Phos-C1 is rationalized by density functional theory studies. 1 Laboratory of Molecular Recognition and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang, P. R. China. 2 State Key Laboratory ✉ of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, P. R. China. email: [email protected]; [email protected] NATURE COMMUNICATIONS | (2021) 12:2416 | https://doi.org/10.1038/s41467-021-22498-1 | www.nature.com/naturecommunications 1 ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-021-22498-1 yrazolones are a vital class of heterocycles possessing various with 84% ee (Fig. 2, entries 1–5). After optimizing the tempera- Pbiological properties1. Of particular interest are the pyr- ture and concentration (Fig. 2, entries 6–11), the reaction at 0.02 azolone derivatives with a chiral center (Fig.
    [Show full text]
  • Chiral Amino–Phosphine and Amido–Phosphine Complexes of Ir and Mg. Catalytic Applications in Olefin Hydroamination
    Zurich Open Repository and Archive University of Zurich Main Library Strickhofstrasse 39 CH-8057 Zurich www.zora.uzh.ch Year: 2016 Chiral amino-phosphine and amido-phosphine complexes of Ir and Mg. Catalytic applications in olefin hydroamination Schmid, Bernhard ; Frieß, Sibylle ; Herrera, Alberto ; Linden, Anthony ; Heinemann, Frank W ; Locke, Harald ; Harder, Sjoerd ; Dorta, Romano DOI: https://doi.org/10.1039/c6dt01146b Posted at the Zurich Open Repository and Archive, University of Zurich ZORA URL: https://doi.org/10.5167/uzh-125944 Journal Article Accepted Version Originally published at: Schmid, Bernhard; Frieß, Sibylle; Herrera, Alberto; Linden, Anthony; Heinemann, Frank W; Locke, Harald; Harder, Sjoerd; Dorta, Romano (2016). Chiral amino-phosphine and amido-phosphine complexes of Ir and Mg. Catalytic applications in olefin hydroamination. Dalton Transactions, 45(30):12028-12040. DOI: https://doi.org/10.1039/c6dt01146b Chiral Amino–Phosphine and Amido–Phosphine Complexes of Ir and Mg. Catalytic Applications in Olefin Hydroamination Bernhard Schmid, † Sibylle Frieß, † Alberto Herrera,† Anthony Linden,‡ Frank W. Heinemann, Harald Locke, Sjoerd Harder, Romano Dorta* Department Chemie und Pharmazie, Anorganische und Allgemeine Chemie, Friedrich–Alexander– Universität Erlangen–Nürnberg, Egerlandstraße 1, 91058 Erlangen, Germany [email protected] ‡) Institut für Chemie, Universität Zürich, Winterthurerstrasse 190, CH-8057, Zurich, Switzerland †) Authors contributed equally to this publication. Abstract The reactions of rac- and (S,S)-trans-9,10-dihydro-9,10-ethanoanthracene-11,12-diamine (ANDEN) with PClPh2 in the presence of NEt3 yield the chiral amino-phosphine ligands rac-6 and (S,S)-6, respectively, on multi-gram scales. Both forms of 6 react quantitatively with MgPh2 to afford the C2– symmetric, N–bound Mg amidophosphine complexes rac-7 and (S,S)-7.
    [Show full text]
  • 402 the Development of an Asymmetric Tsuji Allylation
    402 CHAPTER FOUR The Development of an Asymmetric Tsuji Allylation Reaction† 4.1 Introduction The catalytic asymmetric synthesis of all-carbon quaternary stereocenters stands as a significant challenge in synthetic chemistry.1 Despite the demanding sterics, a number of useful catalytic transformations, including Diels-Alder,2 Heck,3 cyclopropanation,4 alkylation,5 acylation,6 and desymmetrization7 reactions, have been demonstrated to form quaternary stereocenters with good levels of enantioinduction. Although palladium-catalyzed enantioselective allylation chemistry has long been an important asymmetric catalytic tool,8 only recently has palladium (II) -allyl chemistry been used for the formation of quaternary stereocenters. The vast majority of palladium (II) allylic alkylations studied by Trost, Helmchen, Pfaltz, and others form tertiary stereocenters by the attack of malonate anions on prochiral 1,3-disubstituted allyl fragments. Helmchen has shown that such reactions with palladium phosphinooxazoline (PHOX) complexes typically occur via an outer sphere malonate attack at the allyl termini.9 The tendency of palladium to give the less branched products in allylic alkylations with differentially substituted allyl termini makes the formation of quaternary stereocenters on the allyl fragment problematic.10 An alternative, less common strategy in allylic alkylation is the use of prochiral nucleophiles. A quaternary stereocenter may formed on the prochiral nucleophile when it possesses three distinct carbon substituents. A priori, such reactions requiring the remote † This work was performed in collaboration with Justin Mohr, Dr. Andrew Harned, Dr. Kousuke Tani, Dr. Zoltán Novák, Sandy Ma, Nathaniel Sherden, Mike Krout, and Ryan McFadden. 403 chiral ligand to discriminate between the prochiral faces of the incoming nucleophile seem improbable.
    [Show full text]
  • Transition Metal Catalysed Reactions for the Synthesis of Heteroaromatic Compounds
    Transition Metal Catalysed Reactions for the Synthesis of Heteroaromatic Compounds Stephen Christopher Pelly A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg In fulfilment of the requirements for the Degree of Doctor of Philosophy January 2007 DECLARATION I declare that the work presented in this thesis was carried out exclusively by myself under the supervision of Professor C.B. de Koning. It is being submitted for the degree of Doctor of Philosophy in the University of the Witwatersrand, Johannesburg. It has not been submitted before for any degree or examination in any other University. _________________ 27th day of January, 2007 i ABSTRACT The carbazole and 2-isopropenyl-2,3-dihydrobenzofuran structures are widely found in many naturally occurring compounds. For example, the naturally occurring anti-cancer compound, rebeccamycin, contains an indolocarbazole core. Rotenone, which contains an (R)-2-isopropenyl-2,3-dihydrobenzofuran moiety, is widely used today as an effective naturally occurring pesticide. In the carbazole section of this thesis, the synthesis of the naturally occurring furanocarbazole, furostifoline is described. As key steps in this sequence, a Suzuki coupling reaction is utilised to couple appropriately functionalised indole and furan moieties. After further functional group transformations, a metathesis reaction is employed to construct the carbazole system, leading to furostifoline. The synthesis of the unnatural thio-analogue of furostifoline was similarly conducted and is described. Finally, in a somewhat different approach, the synthesis of the indolocarbazole core is described, utilising a Madelung approach initially to form the bis-indole system, 2,2’-biindolyl. After several functional group transformations, a metathesis reaction was once again successfully employed to form the carbazole system, thereby synthesising di(tert-butyl) indolo[2,3-a]carbazole-11,12-dicarboxylate.
    [Show full text]
  • US8513234.Pdf
    USOO851.3234B2 (12) United States Patent (10) Patent No.: US 8,513,234 B2 Isaacs et al. (45) Date of Patent: Aug. 20, 2013 (54) HIV INTEGRASE INHIBITORS 7,217,713 B2 5/2007 Crescenzi et al. 7,232,819 B2 6/2007 Di Francesco et al. 7,273,859 B2 9, 2007 Naidu (75) Inventors: Richt C. E. AARA 7,279.487 B2 10/2007 Egbertson et al. (US), Wayne J. Thompson, Lansdale, 7,414,045 B2 8/2008 Crescenzi et al. PA (US); Peter D. Williams, 7,419,969 B2 9/2008 Naidu et al. Harleysville, PA (US); Dai-Shi Su, 7,435,734 B2 10/2008 Crescenzi et al. Dresher, PA (US); Shankar 7,494.984 B2 2/2009 Banville et al. s s 7,504.405 B2 3/2009 Wang et al. Venkatraman, Lansdale, PA (US); 2004/0229909 A1 1 1/2004 Kiyama et al. Mark W. Embrey, Harleysville, PA 2007/0083045 A1 4/2007 Di Francesco et al. (US); Thorsten E. Fisher, Hatfield, PA 2007/011 1984 A1 5, 2007 Naidu et al. (US); John S. Wai, Harleysville, PA 2007/011 1985 A1 5, 2007 Naidu et al. (US); David C. Dubost, Collegeville, PA (Continued) (US); Richard G. Ball, Edison, NJ (US); Eric J. Choi, Westfield, NJ (US); Tao FOREIGN PATENT DOCUMENTS Pei, Morganville, NJ (US); Sarah L. EP 1698.628 A1 9, 2006 Trice, Glenside, PA (US); Neil WO 2005/061501 A2 7/2005 Campbell, Cherry Hill, NJ (US); (Continued) Matthew Maddess, Boston, MA (US); Peter E. Maligres, Fanwood, NJ (US); OTHER PUBLICATIONS Michael Shevlin, Plainfield, NJ (US); Ferrara et al.
    [Show full text]
  • Asymmetric Hydrogenation of Esters and Efforts Towards Photohydrogenation
    Asymmetric Hydrogenation of Esters and Efforts Towards Photohydrogenation by Riley Thomas Endean A thesis submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy Department of Chemistry University of Alberta © Riley Thomas Endean, 2020 Abstract A thorough overview of esters and their reductions is presented. A large focus was placed on reductions via homogeneous catalytic hydrogenation. Although several ester hydrogenation systems have been developed, the production of highly enantioenriched alcohols has generally relied upon the usage of enantioenriched esters. A system for homogeneous asymmetric hydrogenation of esters to enantioenriched alcohols was discovered and optimized via an in-house screening method. The optimal system 5 6 uses an in situ formed Ru-based catalyst made from [Ru(1-3:5,6-η -C8H11)(η -anthracene)]BF4, the chiral ligand (1R,2R)-N,N′-bis{2-[bis(3,5-dimethylphenyl)phosphino]benzyl}cyclohexane- 1,2-diamine, and H2. This catalyst is highly active and enantioselective towards hydrogenating α-phenoxy esters to β-chiral primary alcohols under mild conditions. The system operates via dynamic kinetic resolution (DKR), where the esters undergo base-assisted racemization and the catalyst preferentially reacts with one enantiomer. Specifically, NaOiPr in THF and NaOEt in DME were optimal base and solvent combinations for the DKR. The alkoxide bases participate in transesterification and catalyst activation. Under 4 atm H2 and at room temperature, the catalyst provides quantitative conversion (50 turnovers) over 1 h for α-phenoxy propionate and butyrate esters (2 mol% catalyst, 50 mol% base). The enantiomeric excesses of the resulting β-chiral alcohols ranged from 79 to 93%.
    [Show full text]
  • Magnetic Hybrid Materials Based on Co/C Nanoparticles and Their Use in Catalysis
    Magnetic Hybrid Materials based on Co/C Nanoparticles and their Use in Catalysis Dissertation Zur Erlangung des Doktorgrades der Naturwissenschaften Dr. rer. nat. der Fakultät für Chemie und Pharmazie der Universität Regensburg vorgelegt von Benjamin Kastl aus Burglengenfeld Regensburg 2018 Die Arbeit wurde angeleitet von: Prof. Dr. Oliver Reiser Promotionsgesuch eingereicht am: 12.06.18 Promotionskolloquium am: Prüfungsauschuss: Vorsitz: Dr. Rainer Müller 1. Gutachter: Prof. Dr. Oliver Reiser 2. Gutachter: Prof. Dr. Rehbein 3. Gutachter: Prof. Dr. Frank-Michael Matysik Der experimentelle Teil der vorliegenden Arbeit wurde im Zeitraum von November 2014 bis November 2017 unter der Anleitung von Prof. Dr. Oliver Reiser am Institut für Organische Chemie der Universität Regensburg angefertigt. Besonders bedanken möchte ich mich bei Herrn Prof. Dr. Oliver Reiser für die Aufnahme in seinen Arbeitskreis, die Überlassung des interessanten Themas, die anregenden Diskussionen und die stete Unterstützung. Meiner Familie “Wissenschaft ist Magie, die funktioniert.” Kurt Vonnegut (1922 – 2007) Table of contents A. Introduction ........................................................................................................................ 4 1. Magnetic nanoparticles: materials and functionalization .............................................. 5 2. Carbon-coated cobalt nanoparticles ............................................................................... 7 3. References ....................................................................................................................
    [Show full text]
  • | Hao Wakat I Maria Del Con at Malaman
    |HAO WAKAT I MARIAUS009937186B2 DEL CON AT MALAMAN NAT (12 ) United States Patent (10 ) Patent No. : US 9 , 937 , 186 B2 Ohlmeyer et al. (45 ) Date of Patent: Apr. 10 , 2018 ( 54 ) SULFONAMIDES DERIVED FROM USPC .. .. .. .. .. 514 / 217 TRICYCLYL - 2 - AMINOCYCLOALKANOLS See application file for complete search history . AS ANTICANCER AGENTS ( 71 ) Applicant: ICAHN SCHOOL OF MEDICINE ( 56 ) References Cited AT MOUNT SINAI, New York , NY U . S . PATENT DOCUMENTS (US ) 4 ,634 ,766 A 1 / 1987 Atkinson et al. (72 ) Inventors : Michael Ohlmeyer , Plainsboro , NJ 4 ,668 ,671 A 5 / 1987 Gribble et al . (US ) ; David Kastrinsky , Fair Lawn, NJ 4 , 882 , 351A 11/ 1989 Oshima et al . 6 ,583 , 138 B1 6 /2003 Miyamoto et al . (US ) 9 , 540 , 358 B2 1 / 2017 Ohlmeyer et al. 2002/ 0103189 A18 / 2002 Miyamoto et al. @(73 ) Assignee : ICAHN SCHOOL OF MEDICINE AT MOUNT SINAI, New York , NY 2008/ 0275023 Al 11/ 2008 Guidi et al . (US ) (Continued ) ( * ) Notice : Subject to any disclaimer , the term of this FOREIGN PATENT DOCUMENTS patent is extended or adjusted under 35 CN 102942562 A 2 /2013 U . S . C . 154 (b ) by 0 days . EP 0679641 A1 11 / 1995 (21 ) Appl. No. : 15 /124 , 891 (Continued ) ( 22 ) PCT Filed : Mar. 10 , 2015 OTHER PUBLICATIONS Zhang et al, “ Akt, FoxO and regulation of apoptosis, ” Biochimica ( 86 ) PCT No .: PCT/ US2015 /019770 et Biophysica Acta , 2011 , vol. 1813 , pp . 1978 -1986 . * $ 371 (c ) ( 1 ) , (Continued ) ( 2 ) Date : Sep . 9 , 2016 (87 ) PCT Pub . No. : WO2015 / 138500 Primary Examiner — Kathrien A Cruz Assistant Examiner — Janet L . Coppins PCT Pub .
    [Show full text]
  • Development of Palladium-Catalyzed Decarboxylative Benzylation Reactions
    Syntheses of Functionalized Benzylic Compounds: Development of Palladium-catalyzed Decarboxylative Benzylation Reactions by Robert Ryan Pangilinan Torregrosa B.S. Chemistry, University of Santo Tomas, Manila Philippines, 2005 Submitted to the Department of Chemistry and the Faculty of the Graduate School of The University of Kansas in partial fulfillment of the requirements for the degree of Doctor of Philosophy _______________________________ Jon A. Tunge, chairperson _______________________________ Paul R. Hanson _______________________________ Richard S. Givens _______________________________ David R. Benson _______________________________ Apurba Dutta Date Defended: July 24, 2012 The Dissertation Committee for Robert Ryan Pangilinan Torregrosa certifies that this is the approved version of the following dissertation: Syntheses of Functionalized Benzylic Compounds: Development of Palladium-catalyzed Decarboxylative Benzylation Reactions _______________________________ Jon A. Tunge, chairperson _______________________________ Paul R. Hanson _______________________________ Richard S. Givens _______________________________ David R. Benson _______________________________ Apurba Dutta Date Defended: July 24, 2012 ii Abstract Robert R. P. Torregrosa Department of Chemistry, July 2012 The University of Kansas Carbon-carbon bond formation between the benzyl carbon and a functional group is important in organic synthesis because majority of the compounds in the chemical literature contain aromatic cores appended with different functionalities
    [Show full text]
  • Molecular Mechanics (MM) 23
    Downloaded from orbit.dtu.dk on: Oct 01, 2021 Selective Homogeneous Catalysis in Asymmetric Synthesis Fristrup, Peter Publication date: 2006 Document Version Publisher's PDF, also known as Version of record Link back to DTU Orbit Citation (APA): Fristrup, P. (2006). Selective Homogeneous Catalysis in Asymmetric Synthesis. Technical University of Denmark. General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. Users may download and print one copy of any publication from the public portal for the purpose of private study or research. You may not further distribute the material or use it for any profit-making activity or commercial gain You may freely distribute the URL identifying the publication in the public portal If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Peter Fristrup Selective Homogeneous Catalysis in Asymmetric Synthesis Ph. D. Thesis DTU, Lyngby, February 2006. Cover: Illustration of the new mnemonic device for prediction of absolute configuration in the osmium- catalyzed asymmetric dihydroxylation. A transition state structure incorporating one of the substrate probes is used to illustrate the molecular structure. ii Peter Fristrup Selective Homogeneous Catalysis in Asymmetric Synthesis Ph.D. Thesis, February 2006 Department of Chemistry Technical University of Denmark iii Preface This thesis is submitted in candidacy for the Ph.D. degree from the Technical University of Denmark (DTU).
    [Show full text]
  • Palladium-Catalyzed Enantioselective Allylic Substitutions on Bifunctional Substrates
    Palladium-catalyzed Enantioselective Allylic Substitutions on Bifunctional Substrates Inauguraldissertation zur Erlangung der Würde eines Doktors der Philosophie vorgelegt der Philosophisch-Naturwissenschaftlichen Fakultät der Universität Basel von Stéphanie Angèle Richoz aus Ursy (FR), Schweiz Basel, 2012 Originaldokument gespeichert auf dem Dokumentenserver der Universität Basel edoc.unibas.ch Dieses Werk ist unter dem Vertrag „Creative Commons Namensnennung-Keine kommerzielle Nutzung-Keine Bearbeitung 2.5 Schweiz“ lizenziert. Die vollständige Lizenz kann unter creativecommons.org/licences/by-nc-nd/2.5/ch eingesehen werden. Genehmigt von der Philosophisch-Naturwissenschaftlichen Fakultät auf Antrag von Prof. Dr. Murat Acemoglu Prof. Dr. Andreas Pfaltz Prof. Dr. Wolf-Dietrich Woggon Basel, den 26. Juni 2012 Prof. Dr. Martin Spiess Dekan Namensnennung-Keine kommerzielle Nutzung-Keine Bearbeitung 2.5 Schweiz Sie dürfen: das Werk vervielfältigen, verbreiten und öffentlich zugänglich machen Zu den folgenden Bedingungen: Namensnennung. Sie müssen den Namen des Autors/Rechteinhabers in der von ihm festgelegten Weise nennen (wodurch aber nicht der Eindruck entstehen darf, Sie oder die Nutzung des Werkes durch Sie würden entlohnt). Keine kommerzielle Nutzung. Dieses Werk darf nicht für kommerzielle Zwecke verwendet werden. Keine Bearbeitung. Dieses Werk darf nicht bearbeitet oder in anderer Weise verändert werden. • Im Falle einer Verbreitung müssen Sie anderen die Lizenzbedingungen, unter welche dieses Werk fällt, mitteilen. Am Einfachsten ist es, einen Link auf diese Seite einzubinden. • Jede der vorgenannten Bedingungen kann aufgehoben werden, sofern Sie die Einwilligung des Rechteinhabers dazu erhalten. • Diese Lizenz lässt die Urheberpersönlichkeitsrechte unberührt. Die gesetzlichen Schranken des Urheberrechts bleiben hiervon unberührt. Die Commons Deed ist eine Zusammenfassung des Lizenzvertrags in allgemeinverständlicher Sprache: http://creativecommons.org/licenses/by-nc-nd/2.5/ch/legalcode.de Haftungsausschluss: Die Commons Deed ist kein Lizenzvertrag.
    [Show full text]