Novel P, N-ligand stabilized transition metal complexes as efficient catalysts for organic syntheses [Elektronische Ressource] / vorgelegt von Benoît Blank

Blank

Informations

• Publié par: universitat_bayreuth
• Publié le: 01 janvier 2009
• Nombre de lectures: 30
• Langue: English
• Poids de l'ouvrage: 1 Mo

Extrait

Novel P,N-Ligand Stabilized
Transition Metal Complexes as Efficient Catalysts
for Organic Syntheses



DISSERTATION



Zur Erlangung des akademischen Grades eines
Doktors der Naturwissenschaften (Dr. rer. nat.)
im Fach Chemie der Fakultät für Biologie, Chemie und Geowissenschaften
der Universität Bayreuth






vorgelegt von
Dipl. Chemiker Benoît Blank
geboren in Frankfurt/Main




Bayreuth, 2009
This thesis fulfills the requirements for the doctoral degree of the Faculty of Biology, Chemistry
and Earth Sciences at the University of Bayreuth.










Thesis submitted: 03.06.2009
Date of Scientific Colloquium: 31.08.2009










Examination Committee:

First referee: Prof. Dr. Rhett Kempe
Second referee: Prof. Dr. Rainer Schobert
Third referee: Prof. Dr. Jürgen Senker
Chairman: Prof. Dr. Thomas Hellweg

This work was carried out from October 2006 to May 2009 at the Chair of Inorganic Chemistry II at
the University of Bayreuth, Germany under the supervision of Professor Dr. Rhett Kempe.






























To my parents, for their constant support

and

to Uli, for her endless patience, encouragement and love…

Abbreviations
Ar aryl
Å Ångström
Bn benzyl
Bu butyl
br broad
°C degree celsius
cod cis-1,5-cyclooctadiene
d doublet
diglyme diethylene glycol dimethyl ether
δ chemical shift (ppm)
equiv equivalent
g gram
GC gas chromatography
h hours
Hz Hertz
Het N-heteroaromatics
J coupling constant (Hz)
K Kelvin
m multiplet
Me methyl
min minute
mL milliliter
mmol millimol
NMR nuclear magnetic resonance
Ph phenyl
Py 2-pyridyl
q quartet
rt room temperature
s singlet
t triplet
μL microliter


Table of Contents
1. Summary ..................................................................................................................................... 1
2. Introduction ................................................................................................................................ 7
3. Overview of Thesis Results...................................................................................................... 11
3.1. Single and Double C−Cl-Activation of Methylene Chloride by P,N-ligand
Coordinated Rhodium Complexes................................................................................. 11
3.2. An Efficient Method for the Selective Iridium-Catalyzed Monoalkylation of
(Hetero)Aromatic Amines with Primary Alcohols........................................................ 12
3.3. Selective Iridium-Catalyzed Alkylation of (Hetero)Aromatic Amines and Diamines
with Alcohols under Mild Reaction Conditions ............................................................ 13
3.4. Synthesis of Selectively Mono-N-Arylated Aliphatic Diamines via Iridium-
Catalyzed Amine Alkylation ......................................................................................... 13
3.5. Catalytic Alkylation of Methyl-N-Heteroaromatics with Alcohols............................... 14
3.6. Individual Contribution to Joint Publications................................................................ 15
4. Single and Double C−Cl-Activation of Methylene Chloride by P,N-ligand
Coordinated Rhodium Complexes.......................................................................................... 17
4.1. Introduction.................................................................................................................... 18
4.2. Results and Discussion .................................................................................................. 19
4.3. Conclusions.................................................................................................................... 28
4.4. Experimental Section..................................................................................................... 28
4.5. References...................................................................................................................... 33
5. An Efficient Method for the Selective Iridium-Catalyzed Monoalkylation of
(Hetero)Aromatic Amines with Primary Alcohols................................................................ 36
5.1. Introduction.................................................................................................................... 37
5.2. Results and Discussion .................................................................................................. 37
5.3. Conclusions.................................................................................................................... 50
5.4. Experimental Section..................................................................................................... 50
5.5. References...................................................................................................................... 54
5.6. Supporting Information ................................................................................................. 56
6. Selective Iridium-Catalyzed Alkylation of (Hetero)Aromatic Amines and Diamines
with Alcohols under Mild Reaction Conditions..................................................................... 71
6.1. Introduction.................................................................................................................... 71
6.2. Results and Discussion .................................................................................................. 72
6.3. Conclusions.................................................................................................................... 87
6.4. Experimental Section..................................................................................................... 87
6.5. References...................................................................................................................... 94
I
7. Synthesis of Selectively Mono-N-Arylated Aliphatic Diamines via Iridium-Catalyzed
Amine Alkylation...................................................................................................................... 97
7.1. Introduction.................................................................................................................... 97
7.2. Results and Discussion .................................................................................................. 98
7.3. Conclusions.................................................................................................................. 105
7.4. Experimental Section................................................................................................... 106
7.5. References.................................................................................................................... 113
8. Catalytic Alkylation of Methyl-N-Heteroaromatics with Alcohols.................................... 117
8.1. Main Text..................................................................................................................... 117
8.2. Experimental Section................................................................................................... 126
8.3. References.................................................................................................................... 127
8.4. Supporting Information ............................................................................................... 128
9. List of Publications................................................................................................................. 148
10. Acknowledgments................................................................................................................... 149
11. Declaration/Erklärung........................................................................................................... 153
II 1. Summary / Zusammenfassung
1. Summary

In the context of this work a library of novel P,N-ligands was synthesized and reacted with several
transition metals with the aim to prepare active complexes for the efficient application in the field of
homogeneous catalysis. Besides the synthesis and full characterization of these P,N-ligand
stabilized transition metal complexes, further important aspects, such as the elucidation of
mechanistic pathways and the development of novel catalytic methodologies for organic syntheses
were covered.
The preparation of the P,N-ligands is carried out in a one-pot reaction, in which first the amine is
selectively deprotonated with n-BuLi and subsequently treated with the corresponding
chlorophosphine. The desired ligand is thus obtained in excellent yields and the reaction can readily
be performed on a multi-gram scale.
1) n-BuLi, -30°C --> rt
2) R PCl, -30°C --> rt2
R'R' N NN N hexane