Transition metal-catalyzed alkoxylation and amination reactions involving propargyl or allyl ...

175 Pages·2017·5 MB·English

by  Daria Diamante

UNIVERSITÀ DEGLI STUDI DELL’INSUBRIA
UNIVERSITÉ PIERRE ET MARIE CURIE

Dipartimento di Scienza e Alta Tecnologia
Ecole Doctorale de Chimie Moléculaire / Equipe ROCS

PhD in Chemical and Natural Sciences XXIX Cycle

Transition Metal-Catalyzed Alkoxylation and Amination
Reactions involving Propargyl or Allyl Derivatives

Thesis of: Daria Diamante
Ph.D. Supervisors: Professor G. Broggini and Professor G. Poli

Academic Year: 2015 / 2016
Ph.D. Dissertation: 13.01.2017
Dedicated to Anna,
my continuous inspiration.
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Acknowledgements

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This work of thesis has been done at the University of Insubria of Como under the
supervision of the Ph.D. coordinator Professor Norberto Masciocchi.

I thank respectfully Professors Paolo Quadrelli, Umberto Piarulli, Louis Fensterbank and Dr Kevin
Cariou for doing me the honor of judging my work of thesis stealing time from their commitments.

At the end of these studies, I want to express a sincere acknowledge to my tutor since a long time
Professor Gianluigi Broggini, friendly called Gianni, from whom I aquired all my knowledges. He
helped and incited me during these years with perseverance. Thank you for your friendliness,
patience and comprehension.

I thank immensely Professor Giovanni Poli, my other tutor, which hosted me in his laboratories for
one year in Paris (University Pierre et Marie Curie). I felt as at home after only a few days. Thank you
for your willingness and for you support.

Morever, my special thanks goes to Dr Julie Oble, without her, it would have been so difficult to
become familiar with the new lab and the new labmates. She has been friendly since the beginning,
she pushed me to be more confident and I felt supported by her in every situation.
At the end of this “adventure”, I go out grown due to this three people. I am grateful for what you
have done for me.

Of course, I thank the entire lab group, both the Italian and the French one for the good atmosphere
in the lab, during our lunches and the coffee breaks. I should mention too many people, to all of you
thank for been there with me when I felt alone or sad or just for laughing together.

Especially, thank you Silvia to be one of my best friends, to be always there for a chemical advice of
for a crazy techno night together  I really felt your lack this year…

In the end, the bigger thanks goes to my friends of a life, Mary, Frenci, Ila, Ste and Marti for
encouraging me every day. Last but not least, the two most important people in my life, Fabio and
Anna.

Yours, Daria
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Table of Contents

Abbreviations pg. 12
Ligands Cited pg. 17
General Introduction pg. 21
Chapter 1: Intramolecular Alkoxylation Reactions pg. 27
1.1. Copper(II)-Catalyzed Alkoxyhalogenation Reactions of Alkynes pg. 30
1.1.1. Aim of this Work pg. 31
1.1.2. Alkoxychlorination Sequence pg. 35
1.1.3. Alkoxybromination and Alkoxyiodination Sequences pg. 37
1.1.4. Exploring Others Substrates pg. 40
1.1.5. Searching for Mechanistic Evidences pg. 41
1.1.6. Conclusions pg.43
Experimental Part pg.46
1.2. Palladium(II)-Catalyzed Oxidative Alkoxyarylation Reactions of Alkenols pg. 73
1.2.1. Introduction / Aim of this Work pg. 74
1.2.2. Optimization pg. 80
1.2.3. Scope pg. 83
1.2.4. Different Organotin Derivatives pg. 85
1.2.5. Applycability of the 7-endo Cyclization pg. 86
1.2.6. Mechnistic Investigation pg. 88
1.2.7. Conclusions pg. 90
Experimental Part pg. 93
Chapter 2: Intermolecular Pd-Catalyzed Allylic Aminations of -Unsaturated Compounds
pg.113
Introduction pg. 115
2.1. Pioneering Works pg. 116
2.2. Direct Intermolecular Allylic Oxylation Reactions pg.119
2.3. Direct Intermolecular Allylic Amination Reactions pg. 124
2.4. Aim of this Work pg. 126
2.5. Direct Oxidative Path {Pd(II) / [Ox]} pg. 128
2.5.1. First Examples and Optimization pg.128
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2.5.2. Scope pg. 129
2.6. Sequential One-Pot Protocol pg. 134
2.6.1. 1st Step: Oxidative Allylic Acyloxylation pg. 134
2.6.2. 2nd Step: Isohypsic Pd(0)-Catalyzed Amination pg. 136
2.7. Conclusions pg. 140
Experimental Part pg. 142
General Conclusions pg. 171

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