A Concise, Enantiospecific Total Synthesis of Chilocorine C Fueled by a Reductive Cyclization/Mannich Reaction Cascade
| Autor: | Scott A. Snyder, Vladislav G. Lisnyak |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
Biological Products
Quinolizidine Pyridines Stereochemistry Molecular Conformation Total synthesis Stereoisomerism Indolizidine General Chemistry 010402 general chemistry 01 natural sciences Biochemistry Catalysis 0104 chemical sciences chemistry.chemical_compound Colloid and Surface Chemistry Monomer chemistry Cyclization Mannich reaction Density Functional Theory Quinolizines |
| Zdroj: | Journal of the American Chemical Society. 142:12027-12033 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/jacs.0c04914 |
| Popis: | Among defensive alkaloids isolated from ladybugs, the heterodimeric member chilocorine C possesses an alluring monomeric unit that combines quinolizidine and indolizidine substructures. Indeed, the overall stereochemical disposition of its ring fusions is distinct from those of related natural products. Herein we show that a carefully orchestrated sequence with several chemoselective transformations, including a designed cascade that accomplishes nine distinct chemical reactions in one-pot, can smoothly forge that domain and ultimately enable a 15-step, 11-pot enantiospecific synthesis of the natural product. Mechanistic studies, density functional theory calculations, and the delineation of several other unsuccessful approaches highlight its unique elements. |
| Databáze: | OpenAIRE |
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