Synthesis, Activation and Catalytic Activity of N-Heterocyclic Carbene Bearing Palladium Catalysts

255 Pages·2013·4.79 MB·English

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University of New Orleans Theses and
Dissertations and Theses
Dissertations
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Oscar Navarro-Fernandez
University of New Orleans
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Navarro-Fernandez, Oscar, "Synthesis, Activation and Catalytic Activity of N-Heterocyclic Carbene Bearing
Palladium Catalysts" (2006). University of New Orleans Theses and Dissertations. 330.
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SYNTHESIS, ACTIVATION AND CATALYTIC ACTIVITY OF
N-HETEROCYCLIC CARBENE BEARING PALLADIUM CATALYSTS

A Dissertation

Submitted to the Graduate Faculty of the
University of New Orleans
in partial fulfillment of the
requirements for the degree of

Doctor of Philosophy
in
The Department of Chemistry

by

Oscar Navarro Fernández

B.Sc. (Hons) Chemistry, Manchester Metropolitan University, 2001
M.S. University of New Orleans, 2003

December, 2005
To my Family, for their love and support

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ACKNOWLEDGEMENTS

I would like to express my endless gratitude to my research advisor Professor
Steven P. Nolan for his guidance and support during all these years working together.
The members of my committee, Professors Bruce C. Gibb, Mark L. Trudell,
Guijun Wang and John B. Wiley, are gratefully acknowledged for their help and time.
Prof. Edwin D. Stevens is acknowledged for his work on the crystal structures, and Dr.
Corinne Gibb is acknowledged for her guidance and assistance with the NMR
experiments.
Prof. Amir H. Hoveyda is gratefully acknowledged for allowing me to make use
of his laboratories at Boston College during the disruption at the University of New
Orleans caused by Hurricane Katrina. The International Precious Metals Institute is
gratefully acknowledged for an Outstanding Student Award 2005.
Finally, I wish to thank to all the past and present members of the Nolan Group
for their help and support: Prof. Rebecca M. Kissling, Prof. Reto Dorta, Dr. Mihai S.
Viciu, Dr. Gabriela A. Grasa, Dr. Fabiano Zinn, Dr. Yoshihiro Oonishi, Dr. Silvia Díez
González, Dr. Natalie M. Scott, and to Pierre de Fremont, Roy A. Kelly, Parisa Mahjoor,
Nicolas Marion, Jianguo Mei and Rohit Singh.

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TABLE OF CONTENTS

List of Tables.....................................................................................................................xi
List of Schemes................................................................................................................xiv
List of Figures..................................................................................................................xvi
Abbreviations...................................................................................................................xix
Abstract..............................................................................................................................xx

Chapter 1. C-C Bond Formation by Cross-Coupling.........................................................1

1.1. Introduction..............................................................................................................1
1.2. Cross-Coupling Reactions.......................................................................................3
1.2.1. Reactions with Organoboron Reagents: The Suzuki-Miyaura
Reaction....................................................................................................3
1.2.1.1. New coupling partners ....................................................................6
1.2.1.2. Palladacycle complexes as catalyst precursors................................9
1.2.1.3. Catalytic systems composed of Pd(0) or Pd(II) derivates and
phosphines......................................................................................11
1.2.1.4. Catalytic systems composed of Pd(0) or Pd(II) derivates
and N- heterocyclic carbenes.........................................................15
1.2.1.5. Ligandless systems.........................................................................18
1.2.1.6. Systems in aqueous media.............................................................19
1.2.1.7. Supported and heterogeneous systems...........................................20
1.2.1.8. Non-palladium based systems........................................................22

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1.2.2. Reactions with Organostannane Reagents:
The Migita-Kosugi-Stille Reaction.........................................................22
1.2.2.1. New coupling partners...................................................................24
1.2.2.2. Palladacycle complexes as catalyst precursors..............................25
1.2.2.3. Catalytic systems composed of Pd(0) or Pd(II) derivates and
phosphines......................................................................................26
1.2.2.4. Catalytic systems composed of Pd(0) or Pd(II) derivates
and N-heterocyclic carbenes..........................................................28
1.2.2.5. Other systems.................................................................................29
1.2.3. Reactions of Terminal Alkynes..............................................................29
1.2.3.1. The Sonogashira coupling reaction................................................31
1.2.3.1.1. Palladacycle complexes and systems composed of
Pd(0) or Pd(II) derivates and N-heterocyclic carbenes.........31
1.2.3.1.2. Catalytic systems composed of Pd(0) or Pd(II)
derivates and phosphines......................................................33
1.2.3.2. Acetylene surrogates......................................................................34
1.2.3.2.1. Alkynylsilicon reagents........................................................34
1.2.3.2.2. Alkynyltin reagents...............................................................35
1.2.3.2.3. Alkynylmagnesium reagents.................................................36
1.2.3.2.4. Alkynylboron reagents..........................................................37
1.2.3.2.5. Alkynylzinc reagents............................................................37
1.2.3.3. The Cadiot-Chodkiewicz reaction.................................................38

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1.2.4. Reactions with Organomagnesium Reagents: The Kumada-Corriu
Reaction..................................................................................................40
1.2.4.1. Nickel-based systems.....................................................................40
1.2.4.2. Iron-based systems.........................................................................42
1.2.4.3. Palladium-based systems...............................................................45
1.2.4.4. Other systems.................................................................................47
1.2.5. Reactions with Organosilicon Reagents: The Hiyama Reaction............48
1.2.5.1. Coupling of arylsilanes..................................................................49
1.2.5.2. Coupling of alkenylsilanes.............................................................51
1.2.5.3. Fluoride-free systems.....................................................................54
1.2.6. Pd or Ni-Catalyzed reactions with Organozinc Reagents:
The Negishi Coupling..............................................................................56
1.2.6.1. Arylzinc reagents...........................................................................58
1.2.6.2. Alkenyl- and alkylzinc derivates...................................................59
1.3. Closing Remarks.....................................................................................................61
1.4. References...............................................................................................................62

Chapter 2. Cross-Coupling and Dehalogenation Reactions Catalyzed by (N-Heterocyclic
Carbene)Pd(allyl)Cl Complexes........................................................................................85

2.1. Introduction............................................................................................................85
2.2. Suzuki-Miyaura Cross-Coupling Reactions..........................................................86
2.3. Catalytic Dehalogenation of Aryl Chlorides..........................................................92
2.4. Aryl Amination of Aryl Triflates...........................................................................96
2.5. Conclusions............................................................................................................98
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2.6. Experimental Section.............................................................................................99
2.6.1. General Considerations...........................................................................99
2.6.2. Conventional and Microwaved-Assisted Suzuki-Miyaura
Cross-Coupling Reaction……………………………………….……………100
2.6.3. Conventional and Microwave-Assisted Catalytic Dehalogenation
of Aryl Chlorides…………………………………..………………….…………105
2.6.4. Catalytic Amination Reactions………………………….…………………….106
2.7. Acknowledgements..............................................................................................108
2.8. References and Notes...........................................................................................108

Chapter 3. General and Efficient Methodology for the Suzuki-Miyaura Reaction in
Technical Grade 2-Propanol............................................................................................113

3.1. Introduction..........................................................................................................113
3.2. Results and Discussion........................................................................................115
3.3. Conclusions..........................................................................................................120
3.4. Experimental Section...........................................................................................120
3.4.1. General Considerations.........................................................................120
3.4.2. Synthesis of Complexes........................................................................121
3.4.3. Suzuki-Miyaura Cross-Coupling Reactions.........................................123
3.4.4. Crystallographic Data...........................................................................123
3.4. Acknowledgements..............................................................................................123
3.5. References............................................................................................................124

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Chapter 4. C-C Bond Formation and Dehalogenation Reactions Catalyzed by a (NHC)-
Bearing Palladacycle (NHC = N-Heterocyclic Carbene).................................................126

4.1. Introduction..........................................................................................................126
4.2. Suzuki-Miyaura Cross-Coupling Reactions........................................................127
4.3. α-Ketone Arylation Reactions.............................................................................135
4.4. Catalytic Dehalogenation Reactions....................................................................138
4.5. Conclusions..........................................................................................................140
4.6. Experimental Section...........................................................................................141
4.6.1. General Considerations.........................................................................141
4.6.2. Suzuki-Miyaura Cross-Coupling of Aryl Chlorides or Triflates
with Phenylboronic Acid......................................................................142
4.6.3. α-Ketone Arylation with Aryl Halides.................................................143
4.6.4. Large Scale α-Ketone Arylation with Aryl Halides.............................149
4.6.5. Microwave-Assisted α-Ketone Arylation with Aryl Halides...............150
4.6.6. Catalytic Dehalogenation of Aryl Chlorides.........................................150
4.7. Acknowledgements..............................................................................................150
4.8. References and Notes...........................................................................................151

Chapter 5. Modified (NHC)Pd(R-Allyl)Cl Complexes (NHC = N-Heterocyclic Carbene)
As Pre-Catalysts for Room Temperature Cross-Coupling Reactions…… ………….……..156

5.1. Introduction..........................................................................................................156
5.2. Results and Discussion........................................................................................158
5.2.1. Synthesis of (IPr)Pd(R-allyl)Cl Complexes..........................................162

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5.2.2. Room temperature Suzuki-Miyaura Coupling Reactions
of Aryl Bromides and Triflates.............................................................166
5.2.3. Room Temperature Suzuki-Miyaura Coupling Reactions
of Aryl Chlorides..................................................................................166
5.2.4. Room Temperature Suzuki-Miyaura Coupling Reactions
of Heterocyclic Chlorides ....................................................................168
5.2.5. Room Temperature Suzuki-Miyaura Coupling Reactions with trans-2-
Phenylvinylboronic Acid......................................................................169
5.2.6. Suzuki-Miyaura Coupling Reactions of Unactivated Aryl Chlorides at
Low Catalyst Loadings.........................................................................172
5.3. Conclusions..........................................................................................................172
5.4. Experimental Section...........................................................................................174
5.4.1. General Information..............................................................................174
5.4.2. Synthesis of (IPr)Pd(R-allyl)Cl complexes..........................................175
5.4.3. Suzuki-Miyaura Cross-Coupling Reactions.........................................176
5.5. Acknowledgements..............................................................................................182
5.6. References and Notes...........................................................................................183

Chapter 6. Large-Scale Synthesis of (NHC)Pd(Allyl)Cl Complexes (NHC = N-
Heterocyclic Carbene).....................................................................................................188

6.1. Introduction..........................................................................................................188
6.2. Results and Discussion........................................................................................190
6.3. Conclusions..........................................................................................................190
6.4. Experimental........................................................................................................191
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