Organocatalytic addition of carbon and oxygen nucleophiles to C-O electrophiles [Elektronische Ressource] / vorgelegt von Torsten Weil

Informations

• Publié par: justus-liebig-universitat_giessen
• Publié le: 01 janvier 2008
• Nombre de lectures: 43
• Langue: Deutsch
• Poids de l'ouvrage: 5 Mo

Extrait

Organocatalytic Addition of Carbon and Oxygen
Nucleophiles to C-O Electrophiles










Kumulativ-Dissertation zur Erlangung des Doktorgrades
der Naturwissenschaftlichen Fachbereiche
(Fachbereich 08 – Biologie und Chemie)
der Justus-Liebig-Universität Giessen



Vorgelegt von
Torsten Weil
aus Siegbach
Giessen 2008






Die vorliegende Arbeit wurde in der Zeit von Juli 2002 bis Februar 2008 am Institut für
Organische Chemie der Justus-Liebig Universität Giessen unter der Anleitung von Herrn
Prof. Dr. Peter R. Schreiner, Ph.D. durchgeführt.






















Ich möchte an dieser Stelle meinem Lehrer, Herrn Prof. Dr. P. R. Schreiner, ganz herzlich für
die interessante Themenstellung, die vielen anregenden Diskussionen, sein stetes Interesse am
Fortgang der Arbeit sowie die erwiesene Unterstützung und zugestandene forscherische
Freiheit im Verlauf der Arbeit danken.

















Für meine Familie






















Organocatalytic Addition of Carbon and Oxygen Nucleophiles to C-O Electrophiles
Contents
1. Transformations of Aldehydes and Ketones to Propargylic Alcohols 1
1.1. Introduction 1
1.2. Representative and established alkynylation methods
using stoichiometric amounts of metal acetylides 2
1.3. Alkynylation reactions using zinc derivatives as reaction promoters 2
1.3.1. Stoichiometric alkynylation reactions using Zn(II) salts 2
1.3.2. Catalytic zinc mediated alkynylation reactions 4
1.3.2.1. Alkynylation reactions using Zn(II) salts
in substoichiometric amounts 4
1.3.2.2. Catalytic alkynylation reactions using dialkylzinc
reagents 6
1.4. Other transition metals as reaction promoters 8
1.4.1. Copper(II) and (I) mediated formation of chiral
tertiary propargylic alcohols 8
21.4.2. Silver(I) catalyzed aldehyde–alkyne (A ) coupling reactions 9
1.4.3. Rhodium-catalyzed aldehyde–alkyne coupling reactions 10
1.4.4. Alkynylations of aromatic aldehydes catalyzed by Titanium
complexs 11
1.5. Indium salt-catalyzed carbonyl alkynylation 12
1.6. Formation of propargylic alcohols mediated by Gallium(III)
compounds 13
1.7. Alkaline bases as reaction promoters 14
1.7.1. Solid base catalyzed reactions 15
1.7.2. Alkoxide-catalyzed alkynylation reactions 15
Organocatalytic Addition of Carbon and Oxygen Nucleophiles to C-O Electrophiles
1.7.3. Alkynylation reactions using cesium hydroxide as catalyst 16
1.8. Alkynylation reactions using non-metal catalytic systems 17
1.8.1. Phosphazene bases as reaction promoters 17
1.8.2. Quaternary ammonium hydroxide base-catalysts 17
1.9. Summary and Outlook 19
2. Alcoholysis of Epoxides 20
2.1. Introduction 20
2.2. Established methods for alcoholysis of epoxides 21
2.3. Epoxide ring opening reactions mediated by BrØnsted acids 21
2.4. Lewis acid catalyzed alcoholysis of epoxides 23
2.5. “ π-Acids” as catalysts for alcoholysis of epoxides 27
2.6. Summary and Outlook 29
3. Formation of 1,3-Dioxolanes 30
3.1. Introduction 30
4. Publications 31
4.1. Organocatalytic alkynylation of aldehydes and ketones under
phase-transfer catalytic conditions 31
4.2. Cooperative BrØnsted acid-type organocatalysis: alcoholysis of
styrene oxides 41
4.3. Organocatalytic formation of 1,3-dioxolanes 47
5. Experimental Section 50
5.1 SI for Organocatalytic alkynylation of aldehydes and
ketones under Phase-transfer catalytic conditions 50
5.2 SI for Cooperative BrØnsted acid-type organocatalysis:
alcoholysis of styrene oxides 62
Organocatalytic Addition of Carbon and Oxygen Nucleophiles to C-O Electrophiles
5.3 SI for Organocatalytic formation of 1,3-dioxolanes 93
6 References 97
7 Bibliography 106
8 Acknowledgement 107
A. Abbreviations and Acronyms 109
B. Compound Index 111

Organocatalytic Addition of Carbon and Oxygen Nucleophiles to C-O Electrophiles