Iron catalyzed C-H activation and synthesis of novel ligands [Elektronische Ressource] / vorgelegt von Masafumi Nakanishi

Masafumi

Informations

• Publié par: rheinisch-westfalischen_technischen_hochschule_-rwth-_aachen
• Publié le: 01 janvier 2007
• Nombre de lectures: 15
• Langue: English
• Poids de l'ouvrage: 1 Mo

Extrait

Iron Catalyzed C-H Activation and Synthesis of Novel Ligands


Von der Fakultät für Mathematik, Informatik und Naturwissenschaften der
Rheinisch-Westfälischen Technischen Hochschule Aachen
zur Erlangung des akademischen Grades eines
Doktors der Naturwissenschaften genehmigte Dissertation

vorgelegt von

Master of Science
Masafumi Nakanishi

aus Kioto (Japan)

Berichter: Universitätsprofessor Dr. C. Bolm
Universitätsprofessor Dr. D. Enders

Tag der mündlichen Prüfung: 8. Oktober 2007

Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfügbar.


























The work reported in this thesis was carried out in the Institute für Organische Chemie der
Rheinisch-Westfälischen Technischen Hochschule Aachen under the supervision of
Universitätsprofessor Dr. Carsten Bolm from April 2004 until October 2007.

I would like to thank Prof. Bolm for giving me the great opportunity to work in his research
group on this interesting topic and his support during my doctoral work.







Part of this work has already been published:


1) “Palladium-Catalyzed N-Arylations of 1,4,7-Triazacyclononanes” M. Nakanishi, C. Bolm,
Adv. Synth. Catal. 2006, 348, 1823.

2) “Iron-Catalyzed Benzylic Oxidation with Aqueous tert-Butyl Hydorperoxide” M. Nakanishi,
C. Bolm, Adv. Synth. Catal. 2007, 349, 861.

3) “Iron-Catalyzed Aziridination ” M. Nakanishi, C. Bolm, Adv. Synth. Catal., in preparation.
















Index 1
Table of Contents

1 Introduction .................................................................................................... 7
1.1 Iron-Catalyzed Reactions .............................................................................................. 8
1.2 Nitrogen Containing Ligands........................................................................................ 8
1.2.1 1,4,7-Triazacyclononane (TACN) Derivatives ....................................................... 9
1.2.2 Dipyridylamine Type Ligands............................................................................... 21
1.3 Genaral Metal-Catalyzed Benzylic Oxidation Chemistry........................................ 23
1.4 Aziridination Chemistry .............................................................................................. 27
1.4.1 Synthesis of α-Aminoketones and -Esters ............................................................ 36
2 Research Objective........................................................................................39
3 Synthesis of Aryl-TACN Derivatives...........................................................42
3.1 N-Arylation of TACN Derivatives .............................................................................. 42
3.1.1 Synthesis of Precursors ......................................................................................... 42
3.1.2 Palladium-Catalyzed N-Arylations........................................................................ 43
3.1.3 Deprotection Methods ........................................................................................... 46
3.1.4 Synthesis of Perfluoroponytailed N-Aryl-TACN.................................................. 47
4 Synthesis of N,N-Dipyridylamino-2-picolylamines...................................49
4.1 Palladium-Catalyzed N-Arylation of Picolylamine Derivatives............................... 49
4.1.1 Synthesis of N-(Pyridin-2-yl)-N-(pyridin-2-ylmethyl)pyridin-2-amine................ 49
4.1.1.1 Palladium-Catalyzed N-Arylation of Picolylamine Derivatives .......................... 50
4.1.1.2 Synthesis of tert-Butyl Substituted Dipyridylpicolylamine Derivatives in C-H
Amidations ............................................................................................................ 52
4.1.1.3 Synthesis of 4-tert-Butylpicolylamine and 2-Chloro-4-tert-butylpyridine.......... 53
4.1.1.4 Synthesis of 4-tert-Butyl substituted 2,2’-Pyridylaminopicoline Derivatives..... 53
4.2 Complexation of N-(Pyridin-2-yl)-N-(pyridin-2-ylmethyl)pyridin-2-amine with
Silver(I) Nitrate .......................................................................................................... 55
4.3 Complexation of Iron(II) Triflate ............................................................................... 57
4.3.1 Complexation of Iron(II) Triflate with N-(Pyridin-2-yl)-N-(pyridin-2-
ylmethyl)pyridin-2-amine...................................................................................... 57
4.3.2 Application in Iron-Catalyzed Oxidation Reactions ............................................. 58
5 Iron-Catalyzed Oxidation Reaction and Nitrogen Transfer Reaction ...59
5.1 Iron-Catalyzed Benzylic Oxidation with TBHP...................................................... 59 Index 2
5.2 Synthesis of Vitamin K ............................................................................................. 65 3
5.3 Iron-Catalyzed Benzylic Oxidation with Hydrogen peroxide................................ 68
5.4 Developement of Iron-Catalyzed Sulfoxide Imination ........................................... 69
5.5 Iron-Catalyzed Aziridination of Olefins .................................................................. 70
5.6 Iron-Catalyzed α-Amination of Silyl Enol Ether Derivatives................................ 80
5.6.1 Synthesis of α-Silaamino acid Derivatives ........................................................... 82
6 Summary and Outlook .................................................................................85
7 Experimental Section....................................................................................90
7.1 General Remarks.......................................................................................................... 90
7.1.1 Techniques............................................................................................................. 90
7.1.2 Solvents ................................................................................................................. 90
7.1.3 Determination of the Physical Properties of the Synthesized Compounds........... 90
7.1.4 Chromatographic Methods .................................................................................... 92
7.1.5 Literature References for Compounds Prepared by Published Procedures........... 93
7.2 Synthesis of Aryl-TACN Derivatives by Palladium Catalysis ................................. 93
7.2.1 N-Arylation of Piperadine ..................................................................................... 93
7.2.2 Synthesis of Triarylated TACN 67a...................................................................... 94
7.2.3 Synthesis of Triarylated TACN 67b ..................................................................... 94
7.2.4 Synthesis of Triarylated TACN 67d ..................................................................... 95
7.2.5 Synthesis of Triarylated TACN 67c...................................................................... 96
7.2.6 Synthesis of Mono-arylated di(Boc) TACN 64b .................................................. 96
7.2.7 Synthesis of Mono-arylated di(Cbz) TACN 64c................................................... 97
7.2.8 Synthesis of Diarylated mono(Ts) TACN 65........................................................ 98
7.2.9 Synthesis of Monoarylated di(Ts) TACN 64a ...................................................... 98
7.2.10 Synthesis of Di(Ts) TACN 62............................................................................. 100
7.2.11 Synthesis of Di(Cbz) TACN 56 .......................................................................... 104
7.2.12 Synthesis of Di(Boc) TACN 24 .......................................................................... 100
7.2.13 Synthesis of TACN 1 .......................................................................................... 101
7.2.14 Synthesis of Mono(Boc) TACN 59..................................................................... 101
7.2.15 Synthesis of Mono(Ts) TACN 61 ....................................................................... 102
7.2.16 Synthesis of Mono(Cbz) TACN 60..................................................................... 102
7.2.17 Synthesis of Tritosyl-TACN 3 ............................................................................ 103
7.2.18 Synthesis of N, N, N-Tritosyl-diethylene triamine 2 ........................................... 103
7.2.19 Synthesis of Perfluoroponytailed-triaryl-TACN 72 ............................................ 104 Index 3

7.3 Synthesis of N-(Pyridin-2-yl)-N-(pyridin-2-ylmethyl)pyridin-2-amine Derivatives
.................................................................................................................................... 105
7.3.1 Representative Procedure 2 for Synthesis of N-[(4-tert-Butylpyridin-2-
yl)methyl]-N-(pyridin-2-yl)p