Iron-Catalyzed Hydrofunctionalisation of Alkenes and Alkynes

Iron-Catalysed Hydrofunctionalisation of Alkenes and Alkynes


Author:
Mark Greenhalgh
Published in: Springer International Publishing
Release Year: 2016
ISBN: 978-3-319-33663-3
Pages: 319
Edition: First Edition
File Size: 21 MB
File Type: pdf
Language: English



Description of Iron-Catalysed Hydrofunctionalisation of Alkenes and Alkynes


Iron-Catalyzed Hydrofunctionalisation of Alkenes and Alkynes The ability to synthesize molecules in a controlled manner is essential for the development of products used in everyday life, such as plastics, fabrics, fertilizers, and pharmaceuticals. With ever-growing global chemical demand and energy consumption, the development of efficient, energy-saving synthetic processes is of paramount importance. Catalysis offers the single most powerful method that can be used to improve the yield and efficiency of molecular synthesis whilst also reducing waste and energy consumption. Iron is one of the most abundant elements on earth and therefore is the ideal choice as a catalyst for future applications.
This work developed novel reactions catalyzed by an inexpensive, non-toxic and environmentally benign iron catalyst. The controlled and efficient synthesis of a range of molecular structures was achieved. Experiments have provided insight into how these reactions work, which should not only provide a greater understanding of the science involved, but also direct future developments towards highly efficient catalysts and catalytic processes.

Content of Iron-Catalysed Hydrofunctionalisation of Alkenes and Alkynes


1 Introduction ......................................... 1
1.1 Hydrofunctionalisation Using Precious Late
Transition-Metal Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2 Hydrofunctionalisation Using Early Transition-Metal
and Main Group Metal Catalysts . . . . . . . . . . . . . . . . . . . . . . . . 6
1.3 Hydrofunctionalisation Using First-Row Transition-Metal
Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.3.1 Nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.3.2 Cobalt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.3.3 Iron. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.4 General Aims . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2 Iron-Catalysed Hydrosilylation of Alkenes and Alkynes. . . . . . . . . . 33
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.2 Results and Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.2.1 State of the Art at the Outset of the Project . . . . . . . . . . . 40
2.2.2 Project Aims . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2.2.3 Methodology Development. . . . . . . . . . . . . . . . . . . . . . . 41
2.2.4 Silane Scope and Limitations . . . . . . . . . . . . . . . . . . . . . 46
2.2.5 Alkene Scope and Limitations . . . . . . . . . . . . . . . . . . . . 47
2.2.6 Hydrosilylation of Alkynes. . . . . . . . . . . . . . . . . . . . . . . 58
2.2.7 Derivatisation of Hydrosilylation Products . . . . . . . . . . . . 64
2.2.8 Preliminary Mechanistic Work . . . . . . . . . . . . . . . . . . . . 66
2.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
3 Iron-Catalysed Hydroboration of Alkenes and Alkynes . . . . . . . . . . 85
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.2 Results and Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.2.1 State of the Art at the Outset of the Project . . . . . . . . . . . 90
3.2.2 Project Aims . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.2.3 Methodology Development. . . . . . . . . . . . . . . . . . . . . . . 91
3.2.4 Hydroboration of Alkenes and Alkynes . . . . . . . . . . . . . . 93
3.2.5 Iron-Catalysed Functionalisation of Alkenes
Using Alternative (Hydro)Functionalisation Reagents. . . . . 101
3.2.6 Preliminary Mechanistic Investigations. . . . . . . . . . . . . . . 102
3.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
4 Iron-Catalysed Hydromagnesiation of Styrene Derivatives. . . . . . . . 115
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
4.1.1 Hydromagnesiation Using Magnesium Hydride. . . . . . . . . 116
4.1.2 Hydromagnesiation Using Grignard Reagents Bearing
β-Hydrogen Atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
4.1.3 Iron-Catalysed Hydromagnesiation . . . . . . . . . . . . . . . . . 123
4.2 Results and Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
4.2.1 State of the Art at the Outset of the Project . . . . . . . . . . . 128
4.2.2 Project Aims . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
4.2.3 Methodology Development. . . . . . . . . . . . . . . . . . . . . . . 129
4.2.4 Investigation of Reaction Mechanism. . . . . . . . . . . . . . . . 139
4.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
5 Experimental. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
5.1 General Experimental. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
5.2 General Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
5.3 Compound Preparation and Characterisation Data . . . . . . . . . . . . 178
5.4 Procedures and Data for Tables and Figures . . . . . . . . . . . . . . . . 268
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304
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