Iron-catalyzed C-N bond formations [Elektronische Ressource] / vorgelegt von Saisuree Prateeptongkum

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Iron-catalyzed C-N bond formations Saisuree Prateeptongkum Rostock, 2010 urn:nbn:de:gbv:28-diss2010-0172-1 Leibniz-Institut für Katalyse e. V. an der Universität Rostock Iron-catalyzed C-N bond formations Kumulative Dissertation zur Erlangung des akademischen Grades Doctor rerum naturalium (Dr. rer. nat.) der Mathematisch-Naturwissenschaftlichen Fakultät der Universität Rostock vorgelegt von Saisuree Prateeptongkum aus Rostock geb. am 20.03.1980 in Phitsanuloke, Thailand Rostock, (11.08.2010) Die vorliegende Arbeit entstand in der Zeit von Juni 2007 bis August 2010 unter der Leitung von Herrn Prof. Dr. Matthias Beller am Leibniz-Institut für Katalyse e.V. an der Universität Rostock.Gutachter:Gutachter 1: Prof. Dr. Matthias Beller Leibniz-Institut für Katalyse e. V. an der Universität RostockGutachter 2: Prof. Dr. Armin Börner V. anGutachter 3: Prof. Dr. Udo KraglInstitut für Chemie, Universität Rostock Tag der Promotion : 02.11.2010 Acknowledgements I would like to express my sincere gratitude to Prof. Dr. Matthias Beller, my supervisor, for giving me the great opportunity to do my PhD in his group as well as for his inspiration, guidance and encouragement throughout the course of this work. I am grateful to Dr. Ralf Jackstell, my group leader for his outstanding cooperation and valuable scientific discussions.

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• Publié par: universitat_rostock
• Publié le: 01 janvier 2010
• Nombre de lectures: 21
• Langue: English
• Poids de l'ouvrage: 1 Mo

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                Iron-catalyzed C-N bond formations                           Saisuree Prateeptongkum   Rostock, 2010           urn:nbn:de:gbv:28-d ss2010-0172-1

 

 

 

 

             

         

    Leibniz-Institut für Katalyse e. V. an der Universität Rostock           Iron-catalyzed C-N bond formations           Kumulative Dissertation   zur Erlangung des akademischen Grades   Doctor rerum naturalium (Dr. rer. nat.)   der Mathematisch-Naturwissenschaftlichen Fakultät   der Universität Rostock    

vorgelegt von   Saisuree Prateeptongkum   aus Rostock   geb. am 20.03.1980 in Phitsanuloke, Thailand  

Rostock, (11.08.2010)    

 

Die vorliegende Arbeit entstand in der Zeit von Juni 2007 bis August 2010 unter der Leitung von Herrn Prof. Dr. Matthias Beller am Leibniz-Institut für Katalyse e.V. an der Universität Rostock.

Gutachter: Gutachter 1: Prof. Dr. Matthias Beller Leibniz-Institut für Katalyse e. V. an der Universität Rostock Gutachter 2: Prof. Dr. Armin Börner Leibniz-Institut für Katalyse e. V. an der Universität Rostock Gutachter 3: Prof. Dr. Udo Kragl Institut für Chemie, Universität Rostock

Tag der Promotion : 02.11.2010

 

 

Acknowledgements     I would like to express my sincere gratitude toProf. Dr. Matthias Beller, my supervisor, for giving me the great opportunity to do my PhD in his group as well as for his inspiration, guidance and encouragement throughout the course of this work.   I am grateful toDr. Ralf Jackstell, my group leader for his outstanding cooperation and valuable scientific discussions.   I also would like to express my appreciation toDr. Irina Jovelfor her helpful comments and suggestions. Thanks are also extendedto Dr. Kathrin Junge andDr. Henrik Junge for providing a pleasant working environment during my stay in their laboratory.   In addition, I would like to thank all the member of the Beller group for their useful discussions and friendship which have made my time in Germany a pleasant and worthwhile experience. My special thanks go toIlona Stahr,Dr. Holger Klein,Cathleen Buch,Anne Grotevendt,Irene Piras,Maribel Bartolomè,Reiko Jennerjahn,Christopher Federsel,Katrin- Marie Driller andDaniya Fatkulina, my colleagues, for their kind support. I am thankful to Björn Loges,Giulia Erre,Daniele Addis,Thomas Schulz andChristian Torborg their for generous help.   I greatly appreciate and wish to thankDr. Christine Fischer,Dr. Anke Spannenberg,Susanne Buchholz,Susanne Schareina,Andreas Kochthe analytical team for their great and all assistance throughout this work.   I deeply acknowledge Thammasat University, Thailand for financial support.   Finally, this thesis would not been possible without love and encouragement of my parents. Also, big thanks to my sisters and brother for all of their support as well as my friends for their friendship and support throughout my time in Germany.        

 

 

 

 

 

     

 

University of Rostock Abstract  

Iron-catalyzed C-N bond formations 

 

Saisuree Prateeptongkum Leibniz-Institut für Katalyse e.V. an der Universität Rostock     This thesis is mainly concerned with the development and application of iron-catalyzed reactions for the synthesis of nitrogen-containing organic compounds. Oximes were synthesized by a novel iron-catalyzed nitrosation of olefins withtert-butyl nitrite and sodium borohydride. Succinimides and maleimides were prepared by employing an iron-catalyzed carbonylation of internal alkynes with ammonia as a key step. This efficient method was applied for the synthesis of natural products and interesting organic building blocks. Furthermore, the thesis describes the development of an efficient protocol for the synthesis of various nitroolefins. Finally, a synthesis of propargyl amines by Shvo-catalyzed alkynylation reaction is presented.   Die vorliegene Dissertation beschäftigt sich hauptsächlich mit der Entwicklung und der Anwendung von eisenkatalysierten Reaktionen für die Synthese von stickstoffhaltigen organischen Verbindungen. So gelang es, Oxime in einer neuartigen eisenkatalysierten Nitrosierung von Olefinen mittert-Butylnitrit und Natriumborhydrid herzustellen. Succinimide und Maleimide konnten unter Verwendung von eisenkatalysierten Carbonylierungen interner Alkine mit Ammoniak als Schlüsselschitt generiert werden. Diese sehr effiziente Methode wurde mit interessanten organischen Bausteinen auf die Synthese von Naturstoffen übertragen. Darüberhinaus beschreibt diese Dissertation die Entwicklung eines effizienten Syntheseprotokolls für die Darstellung   verschiedener Nitroolefine. Zusätzlich wird auch die Synthese von Propargylaminen unter Verwendung von Shvo-katalysierten Alkinierungsreaktionen vorgestellt.    

 

 

Table of contents 1 Introduction 2 Iron-catalyzed C-N bond formations 2.1 Addition reactions 2.1.1 Aza-Michael additions 2.1.2 Hydroaminations of non-activated alkenes and alkynes 2.1.3 Alkene diaminations 2.1.4 Aminochlorinations 2.1.5 Aminohydroxylations 2.2 Cycloadditions 2.2.1 [2+1]-Cycloadditions (Aziridinations) 2.2.2 [2+2]-Cycloadditions 2.2.3 [2+3]-Cycloadditions 2.2.4 [4+1]-Cycloadditions 2.2.5 [2+2+1]-Cycloadditions 2.2.6 [2+1+1+1]-Cycloadditions 2.2.7 1,3-Dipolar cycloadditions 2.3 Substitution reactions 2.3.1 Nucleophilic substitution of non-activated C-X bonds 2.3.2   Allylic and propargylic aminations 2.3.3N-Arylations 2.4 The use of iron-catalyzed reactions in natural product synthesis 2.4.1 Iron-mediated synthesis of alkaloids 2.4.2 Iron-catalyzed synthesis of octapamine 2.4.3 Iron-catalyzed synthesis of maleimides 2.5 Miscellaneous 2.5.1 Oximations 2.5.2 Paal-Knorr pyrrole synthesis 2.5.3 Rearrangements  

1 2 2 2 3 6 8 9 11 11 15 15 16 16 17 18 19 19 20 25 31 31 35 35 36 36 37 37

 

2.6 3  

4

4.1 4.2 4.3 4.4 4.5 5

 

References Objectives of this work

Publications

 

A selective and practical synthesis of nitroolefins First iron-catalyzed synthesis of oximes from styrenes  amines: ruthenium-catalyzed-Functionalization of non-activated alipha tic alkynylations and alkylations Efficient synthesis of biologically interesting 3,4-diaryl-substituted succinimides and maleimides: application of iron-catalyzed carbonylations Iron-catalyzed carbonylation as a key step in the short and efficient synthesis of himanimide A and B Summary

39 50  

51

51 57 61 65 76 81

 

Abbreviations Ac acac Ar Bn Boc i-Bu t-Bu cat. CBz Cp DCE DDQ (DHQD) 2 Pyr dmeda DMF DMSO dr   ee emim BTA equiv Et h n-Hex Me min MS MW Ns Nu OTf

Abbreviations

Acetyl Acetonylacetate Aryl group Benzyl tert-Butyloxycarbonyl   iso-Butyl tert-Butyl Catalyst Carboxybenzyl 5 -Cyclopentadienyl 1,2-dichloroethane 2,3-Dichloro-5,6-dicyanobenzoquinone Hydroquinidine-2,5-diphenyl-4,6-pyrimidinediyl diether N,N’-Dimethylethane-1,2-diamine N,N-Dimethylformamide Dimethyl sulfoxide Diastereomeric ratio Enantiomeric excess Ethylmethylimidazolium bis[(trifluoromethyl)sulfonyl]amide Equivalent  Ethyl Hour n-Hexyl Metyl Minute Molecular sieves Microwave 4-Nitrobenzenesulfonyl  Nucleophile  Triflate (trifluoromethanesulfonate)

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