Development of Novel Routes and Methods for the Semisynthesis of the Marine Steroid Demethylgorgosterol and Unnatural Analogs
Nicolai Rosenbaum
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Nicolai Rosenbaum, Development of Novel Routes and Methods for the Semisynthesis of the Marine Steroid Demethylgorgosterol and Unnatural Analogs (2022), Logos Verlag, Berlin, ISBN: 9783832584597
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Description / Abstract
Gorgosterol and its derivative demethylgorgosterol are two long known marine steroids with unusual properties and a unique structure, containing a cyclopropane moiety in the side chain. Gorgosterol and its derivatives show diverse structural motives and biological activities. Moreover, corals and coral reefs have a tremendous ecological and economic impact but are endangered by climate change. A better understanding of corals can therefore aid their protection and conservation.
A concise and high yielding formal semisynthesis for the marine steroid demethylgorgosterol was developed. Centerpiece was a stereoselective intermolecular cyclopropanation. A variety of demethylgorgosterol analogs were synthesized for biological applications. These include hydrocarbon analogs, diversely functionalized analogs, and fluorophore-steroid conjugates to track and visualize steroids in vivo. Finally, a new method for the synthesis of 3-cyclopropylacrylates was developed. Here, a vinylogous diazoester was utilized to cyclopropanate alkenes. The observed cis-selectivity was explained with Ï-Ï-interactions in the transition state.
A concise and high yielding formal semisynthesis for the marine steroid demethylgorgosterol was developed. Centerpiece was a stereoselective intermolecular cyclopropanation. A variety of demethylgorgosterol analogs were synthesized for biological applications. These include hydrocarbon analogs, diversely functionalized analogs, and fluorophore-steroid conjugates to track and visualize steroids in vivo. Finally, a new method for the synthesis of 3-cyclopropylacrylates was developed. Here, a vinylogous diazoester was utilized to cyclopropanate alkenes. The observed cis-selectivity was explained with Ï-Ï-interactions in the transition state.
Table of content
- BEGINN
- 1 Introduction
- 1.1 Steroids[11]
- 1.2 Gorgosterol
- 2 Aim of this work
- 3 Results and discussion
- 3.1 Towards a new semisynthesis of demethylgorgosterol and gorgosterol
- 3.2 Synthesis of demethylgorgosterol analogs
- 3.3 3-Cyclopropylacrylates by cyclopropanation using a vinylogous diazoester
- 4 Summary and outlook
- 4.1 Development of a new semisynthesis of demethylgorgosterol and gorgosterol[26]
- 4.2 Synthesis of demethylgorgosterol analogs
- 4.3 3-Cyclopropylacrylates by cyclopropanation using a vinylogous diazo ester
- 5 Experimental
- 5.1 General information
- 5.2 Synthetic methods and characterization data
- 5.3 Crystallographic data
- 6 References
- 7 Appendix
- 7.1 List of abbreviations and acronyms
- 7.2 Curriculum vitae
- 7.3 List of publications
- 7.4 Acknowledgments