Metal-Catalyzed Nࢀ“H and Oࢀ“H Insertion from alpha-Diazocarbonyl Compounds
Yuling Hu
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Yuling Hu, Metal-Catalyzed Nࢀ“H and Oࢀ“H Insertion from alpha-Diazocarbonyl Compounds (2019), Logos Verlag, Berlin, ISBN: 9783832587543
Beschreibung / Abstract
Transition-metal catalyzed X-H insertions from alpha-diazocarbonyl compounds represent one of the most efficient approaches to form C--X bonds. The presented thesis is based on the synthesis and application of alpha-diazocarbonyl compounds in metal-catalyzed N-H insertion and the chemoenzymatic synthesis of heterocycles via a [Cu]/[Rh] catalyzed intramolecular O-H insertion.
In the first part, a straightforward approach via the Wittig reaction, gamma-Umpolung addition and diazo transfer reaction allowed the synthesis of unsaturated alpha-diazocarbonyl compounds with ease.
In the second part, the newly synthesized (R textsubscript{p)-pseudo-ortho [2.2]paracyclophane-based bisoxazoline ligands presented superior reactivity. The obtained delta-amino alpha,beta-unsaturated carboxylic esters were used to synthesize hexahydroindoles, which are key intermediates in the synthesis route of Rostratin B-D.
Additional investigation of alpha-diazocarbonyl compounds led to the enzymatic synthesis of O-Heterocycles. With the employment of enantiopure starting material obtained from ketoreductase LbADH, the enantioselectivity of each diastereomer from the O-H insertion product have been effectivity improved.
In the first part, a straightforward approach via the Wittig reaction, gamma-Umpolung addition and diazo transfer reaction allowed the synthesis of unsaturated alpha-diazocarbonyl compounds with ease.
In the second part, the newly synthesized (R textsubscript{p)-pseudo-ortho [2.2]paracyclophane-based bisoxazoline ligands presented superior reactivity. The obtained delta-amino alpha,beta-unsaturated carboxylic esters were used to synthesize hexahydroindoles, which are key intermediates in the synthesis route of Rostratin B-D.
Additional investigation of alpha-diazocarbonyl compounds led to the enzymatic synthesis of O-Heterocycles. With the employment of enantiopure starting material obtained from ketoreductase LbADH, the enantioselectivity of each diastereomer from the O-H insertion product have been effectivity improved.
Inhaltsverzeichnis
- BEGINN
- 1 Abstract
- 2 Introduction
- 2.1 Synthesis of α-Diazocarbonyl Compounds
- 2.2 Application of α-Diazocarbonyl Compounds in Metal-Catalyzed X–H (X = N, O) Insertion Reactions
- 2.3 Development of Enantioselective X–H Insertion Reactions
- 2.4 Paracyclophane Derivatives in Asymmetric Catalysis
- 2.5 Enzymes as Efficient Biocatalysts in the Asymmetric Reduction of Ketones
- 3 Aim of the Work
- 4 Results and Discussion
- 4.1 Synthesis of α-Diazocarbonyl Compounds
- 4.2 [2.2]Paracyclophane-based Ligands in Metal-Catalyzed N–H Insertion Reactions
- 4.3 Metal-catalyzed N–H Insertion with [2.2]Paracyclophane Ligands
- 4.4 Chemoenzymatic Synthesis of O-Containing Heterocycles via Ketoreductasecatalyzed Highly Enantioselective Reduction
- 5 Summary and Outlook
- 5.1 Synthesis of α-Diazocarbonyl Compounds
- 5.2 [2.2]Paracyclophane-based Catalysts and Metal-catalyzed N–H Insertion Reactions
- 5.3 Chemoenzymatic Synthesis of O-Containing Heterocycles via Ketoreductasecatalyzed Highly Enantioselective Reduction
- 6 Experimental Part
- 6.1 General Information on [2.2]Paracyclophane
- 6.2 Synthesis and Characterization
- 7 List of Abbreviations
- 8 Literature
- 9 Appendix
- 9.1 X-ray Crystallographic data
- 9.2 Curriculum Vitae
- 9.3 Publications and Conference Contributions
- 9.4 Acknowledgement