Iron-catalyzed C-N bond formations [Elektronische Ressource] / vorgelegt von Saisuree Prateeptongkum
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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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Published 01 January 2010
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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)2Pyr 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)
i